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Abstract:

The present invention relates to compositions and processes of making and
using interpolymers having a controlled molecular weight distribution.
Multilayer films and film layers derived from novel
ethylene/α-olefin interpolymers are also disclosed.

Claims:

1. (canceled)

2. An ethylene/α-olefin interpolymer which has (i) a DSC curve
characterized by an area under the DSC curve from the melting peak
temperature to the end of melting is at least about 17% of the total area
under the DSC melting curve from -20.degree. C. to the end of melting;
(ii) a density from about 0.875 g/cc to about 0.915 g/cc; and (iii) a
I10/I2 from 5.5 to 6.5.

3. The ethylene/α-olefin interpolymer of claim 2 having less than
0.01 long chain branches per 1000 carbon atoms.

4. The ethylene/α-olefin interpolymer of claim 2 which has a DSC
curve characterized by an area under the DSC curve from the melting peak
temperature to the end of melting is at least about 18% of the total area
under the DSC melting curve from -20.degree. C. to the end of melting.

5. The ethylene/α-olefin interpolymer of claim 2 which has a DSC
curve characterized by an area under the DSC curve from the melting peak
temperature to the end of melting is from at least about 18% to about 35%
of the total area under the DSC melting curve from -20.degree. C. to the
end of melting.

6. The ethylene/α-olefin interpolymer of claim 2 which has a DSC
curve characterized by an area under the DSC curve from the melting peak
temperature to the end of melting is at least about 20% of the total area
under the DSC melting curve from -20.degree. C. to the end of melting.

7. The ethylene/α-olefin interpolymer of claim 2 which has a
density from about 0.895 g/cc to about 0.910 g/cc.

8. The ethylene/α-olefin interpolymer of claim 2 wherein the
I10/I2 is from about 5.6 to about 6.3.

9. The ethylene/α-olefin interpolymer of claim 2 wherein the
interpolymer has a molecular weight distribution in the range from about
2.0 to about 3.8.

10. The ethylene/α-olefin interpolymer of claim 2 wherein the
interpolymer has a molecular weight distribution in the range from about
2.2 to about 2.8.

11. The ethylene/α-olefin interpolymer of claim 2 which has a B
value of greater than about 0.98.

12. A film comprising: an ethylene/α-olefin interpolymer which has
(i) a DSC curve characterized by an area under the DSC curve from the
melting peak temperature to the end of melting is at least about 17% of
the total area under the DSC melting curve from -20.degree. C. to the end
of melting; (ii) a density from about 0.875 g/cc to about 0.915 g/cc; and
(iii) a I10/I2 from 5.5 to 6.5.

13. The film of claim 12 wherein the ethylene/α-olefin interpolymer
has less than 0.01 long chain branches per 1000 carbon atoms.

14. The film of claim 12 wherein the ethylene/α-olefin interpolymer
has a density from about 0.895 g/cc to about 0.910 g/cc.

15. The film of claim 12 wherein the ethylene/α-olefin interpolymer
has a I10/I2 from about 5.6 to about 6.3.

16. A multilayer film comprising: a) a base layer comprising a first
polymer; b) a tie layer comprising a second polymer; and c) a sealant
layer comprising an ethylene/α-olefin interpolymer, wherein the tie
layer is between the base layer and the sealant layer and wherein the
ethylene/α-olefin interpolymer of the sealant layer has (i) DSC
curve characterized by an area under the DSC curve from the melting peak
temperature to the end of melting is at least about 17% of the total area
under the DSC melting curve from -20.degree. C. to the end of melting;
(ii) a density from about 0.875 g/cc to about 0.915 g/cc; and (iii) a
I10/I2 from 5.5 to 6.5.

17. The multilayer film of claim 16 wherein the ethylene/α-olefin
interpolymer has 0.01 long chain branches per 1000 carbon atoms.

18. The ethylene/α-olefin interpolymer of claim 16 which has a
density from about 0.895 g/cc to about 0.910 g/cc.

19. The ethylene/α-olefin interpolymer of claim 16 wherein the
I10/I2 is from about 5.6 to about 6.3.

Description:

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a Continuation of U.S. application Ser. No.
11/762, 643, filed on Jun. 13, 2007, which is a Continuation-In-Part
Application of U.S. application Ser. No. 11/608,171, filed on Dec. 7,
2006, which claims the benefit under 35 U.S.C 119(e) of U.S. Provisional
Application No. 60/749,308, filed Dec. 9, 2005, both of which are herein
incorporated by reference in their entirety.

FIELD OF THE INVENTION

[0002] The present invention relates to ethylene/α-olefin
interpolymer compositions having a controlled molecular weight
distribution and methods of making and using the compositions. More
particularly, the invention relates to using the ethylene/α-olefin
interpolymer compositions in multilayer films.

BACKGROUND OF THE INVENTION

[0003] It is desirable to produce ethylene/α-olefin interpolymer
compositions of controlled molecular weight distribution in a
cost-effective manner. In particular ethylene/α-olefin interpolymer
compositions having a multi-modal (two or more modes wherein the case of
two may interchangeably be referred to as bimodal or multi-modal)
molecular weight distribution are often desirable for some applications,
for example, pipes for natural gas, sewers, mining, etc. Also, some
applications may require compositions wherein a low molecular weight
portion of the ethylene/α-olefin interpolymer composition has a
higher density than a high molecular weight portion of the
ethylene/α-olefin interpolymer composition. Unfortunately, to date
the available processes do not effectively and efficiently control the
distribution or result in compositions with the desired density and
molecular weight combinations. Therefore, there is a need for processes
that can control the molecular weight distribution or result in
compositions with the desired density and molecular weight combinations.
There is also a need for interpolymers having improved properties, e.g.,
heat seal and residual enthalpy, as well as, improved film layers and
films having such properties.

SUMMARY OF THE INVENTION

[0004] New processes have been discovered which result in effective
control of molecular weight distribution. Advantageously, the inventive
processes may be designed to result in compositions wherein a low
molecular weight portion of the ethylene/α-olefin interpolymer
composition has a higher density than a high molecular weight portion of
the ethylene/α-olefin interpolymer composition. Also, the
ethylene/α-olefin interpolymer composition may be produced in a
single polymerization reactor and/or using a single catalyst. Novel
compositions often may result from the aforementioned processes. The
novel compositions comprise an ethylene/α-olefin interpolymer
composition with a multi-modal molecular weight distribution and one or
more molecules having a gram molecular weight equal to about ((the
molecular weight of an aryl or hydrocarbyl-ligand of a
pre-catalyst)+28+14*X), wherein X represents an integer from zero to 10,
preferably zero to 8.

[0005] Novel multilayer films have been discovered that comprise: [0006]
(A) a base layer comprising a first polymer; [0007] (B) a tie layer
comprising a second polymer; and [0008] (C) a sealant layer comprising an
ethylene/α-olefin interpolymer, wherein the tie layer is between
the base layer and the sealant layer and wherein the
ethylene/α-olefin interpolymer of the sealant layer has a DSC curve
characterized by an area under the DSC curve from the melting peak
temperature to the end of melting is at least about 17% and, in most
cases at most about 50%, of the total area under the DSC melting curve
from -20° C. to the end of melting. The interpolymer may have a B
value of greater than 0.98. Novel film layers have also been discovered
that comprise one or more novel ethylene/α-olefin interpolymers
having a DSC curve characterized by an area under the DSC curve from the
melting peak temperature to the end of melting is at least about 17%,
preferably at least 18%, of the total area under the DSC melting curve
from -20° C. to the end of melting. Novel ethylene/α-olefin
interpolymers have been discovered that comprise the following
characteristics: a density in g/cc, d, and a weight percent
α-olefin, Wt. %, wherein the numerical values of d and Wt. %
correspond to the relationship: d≦-0.0018 Wt. %+0.9297 and/or the
relationship d≦-0.0019 Wt. %+0.933.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] FIGS. 1-14 are a series of slides explaining multi-site behavior in
copolymerizations.

[0017] FIG. 29 is a plot showing the density of an ethylene/α-olefin
interpolymer as a function of the weight percentage of 1-octene for
inventive polymers made using diethyl zinc (DEZ) and inventive polymers
made without using DEZ.

[0018]FIG. 30 is a graph showing the average hot tack force (N), i.e.,
average hot tack strength, of the inventive multilayer films of BB and CC
vs. comparative multilayer films of DD and EE.

[0019] FIG. 31 is a graph showing the average hot tack force (N), i.e.,
average hot tack strength, of the inventive multilayer films of MM and NN
vs. comparative multilayer films of OO and PP.

[0020]FIG. 32 is a graph showing a comparison of the average peak load
and average total energy for an oriented film comprising the interpolymer
of Example 22 and an oriented film comprising Comparative Polymer G.

DETAILED DESCRIPTION OF THE INVENTION

General Definitions

[0021] If and when employed herein, the following terms shall have the
given meaning for the purposes of this invention:

[0022] "Polymer" refers to a polymeric compound prepared by polymerizing
monomers, whether of the same or a different type. The generic term
"polymer" embraces the terms "homopolymer," "copolymer," "terpolymer" as
well as "interpolymer."

[0023] "Interpolymer" refers to a polymer prepared by the polymerization
of at least two different types of monomers. The generic term
"interpolymer" includes the term "copolymer" (which is usually employed
to refer to a polymer prepared from two different monomers) as well as
the term "terpolymer" (which is usually employed to refer to a polymer
prepared from three different types of monomers). It also encompasses
polymers made by polymerizing four or more types of monomers.

[0024] "Multi-block copolymer" or "multi-block interpolymer" refers to a
polymer comprising two or more chemically distinct regions or segments
(referred to as "blocks") preferably joined in a linear manner, that is,
a polymer comprising chemically differentiated units which are joined
end-to-end with respect to polymerized ethylenic functionality, rather
than in pendent or grafted fashion. In a preferred embodiment, the blocks
differ in the amount or type of comonomer incorporated therein, the
density, the amount of crystallinity, the crystallite size attributable
to a polymer of such composition, the type or degree of tacticity
(isotactic or syndiotactic), regio-regularity or regio-irregularity, the
amount of branching, including long chain branching or hyper-branching,
the homogeneity, or any other chemical or physical property. The
multi-block copolymers are characterized by unique distributions of
polydispersity index (PDI or Mw/Mn), block length distribution,
and/or block number distribution due to the unique process of making the
copolymers. More specifically, when produced in a continuous process, the
multi-block polymers often possess PDI from about 1.7 to about 2.9, from
about 1.8 to about 2.5, from about 1.8 to about 2.2, or from about 1.8 to
about 2.1.

[0025] "Density" is tested in accordance with ASTM D792.

[0026] "Melt Index (I2)" is determined according to ASTM D1238 using
a weight of 2.16 kg at 190° C. for polymers comprising ethylene as
the major component in the polymer.

[0027] "Melt Flow Rate (MFR)" is determined for according to ASTM D1238
using a weight of 2.16 kg at 230° C. for polymers comprising
propylene as the major component in the polymer.

[0028] "Molecular weight distribution" or MWD is measured by conventional
GPC per the procedure described by T. Williams and I. M. Ward, Journal of
Polymer Science, Polymer Letters Edition (1968), 6(9), 621-624, wherein
Coefficient B is 1 and Coefficient A is 0.4316.

[0029] "Multilayer film" refers to a film having at least two layers.

[0030] "Tie layer" refers to an intermediate layer of a multilayer film
wherein the intermediate layer can promote the adhesion between two
adjacent layers of the intermediate layer.

[0031] "Sealant layer" refers to a layer of a multilayer film wherein the
layer comprises a material capable of sealing. Typically, such sealing
may occur upon exposure to, for example, heat. In some embodiments, the
sealant layer is an outermost layer of the multilayer film.

[0032] "Base layer" refers to a substrate of a multilayer film wherein the
substrate forms the base of the film.

[0033] A layer or multilayer film that is "substantially free" of an
additive or a compound refers to a layer or multilayer film containing
less than 20 wt. %, less than 10 wt. %, less than 5 wt. %, less than 4
wt. %, less than 3 wt. %, less than 2 wt. %, less than 1 wt. %, less than
0.5 wt. %, less than 0.1 wt. %, or less than 0.01 wt. % of the additive
or compound, based on the total weight of the layer or multilayer film.

[0034] In the following description, all numbers disclosed herein are
approximate values, regardless whether the word "about" or "approximate"
is used in connection therewith. They may vary by 1 percent, 2 percent, 5
percent, or, sometimes, 10 to 20 percent. Whenever a numerical range with
a lower limit, RL, and an upper limit, RU, is disclosed, any
number falling within the range is specifically disclosed. In particular,
the following numbers within the range are specifically disclosed:
R=RL+k*(RU-RL), wherein k is a variable ranging from 1
percent to 100 percent with a 1 percent increment, i.e., k is 1 percent,
2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent, 51
percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98
percent, 99 percent, or 100 percent. Moreover, any numerical range
defined by two R numbers as defined in the above is also specifically
disclosed.

Controlling Molecular Weight and Density

[0035] It has been discovered that the molecular weight distribution of a
resulting polymer may be controlled. For example, using the proper
reaction conditions (e.g., a well mixed homogeneous reaction environment,
a steady-state concentration of two or more monomers such as ethylene and
an α-olefin like octene, and a proper pre-catalyst or catalyst) the
bimodal molecular weight "split" of the polymer may be controlled by the
mole fractions (f) of the two or more monomers, n, such that the mole
fraction of monomer m is defined as:

f m = [ Monomer m ] i = 1 n [ Monomer i ] .
##EQU00001##

[0036] That is, the molecular weight split can be controlled so that it is
basically a function of the relative monomer concentrations in solution.
These same relative monomer concentrations also, depending upon the
reaction conditions, may determine the overall composition (i.e. density)
of the total polymer.

[0037] One aspect of controlling monomer purity useful herein is by
utilizing a side stream of monomer in contact with a selected catalyst in
a plug flow reactor. If the monomer is impure, then a lower than expected
exotherm will be observed in the plug flow reactor. In this manner,
monomer purity is monitored and adjusted if necessary.

[0038] While not wishing to be bound by any theory the Applicants have
discovered that the reason that the monomer concentration:molecular
weight split relationship can be made to occur is that a different
catalyst species can be made from each monomer reactant. This means that
a lower molecular weight polymer is formed by an "ethylene-inserted" form
of the catalyst, while an "α-olefin-inserted" form of the catalyst
gives a higher molecular weight polymer. Advantageously, this results in
a molecular weight split which is controlled by controlling the relative
amounts of the various catalyst species that are formed.

[0039] As an example it is believed that the Hafnium catalyst below can be
made to form an ethylene-inserted cation and an octene-inserted cation in
the presence of ethylene and octene and the proper reaction conditions
including, for example, a well mixed homogeneous reaction environment.

##STR00001##

[0040] Therefore, the present invention allows one to control the
molecular weight split in numerous ways. One method of the present
invention involves changing the ligand structure of a given catalyst to
affect the resulting split for a given overall density copolymer. Thus,
one may select suitable pre-catalyst(s) for the polymerization to control
the concentrations of an ethylene-inserted cation and/or an
octene-inserted cation and thereby control the resulting molecular weight
split. Alternatively, the present invention allows one to control the
polymer split from a given catalyst precursor. For example, one such
method would be to do a pre-reaction or pre-polymerization of sorts,
e.g., contacting a pre-catalyst with a single monomer to generate the
desired catalyst species concentrations, then feeding part or all of this
pre-reaction product to the reactor. This could optionally be done with
the addition of pure pre-catalyst, providing a high degree of control
over the resulting polymer bimodality.

##STR00002##

[0041] In yet another alternative of the present invention, the polymer
split can be modified by changing process variables. For example, one can
control the amount of inserted catalyst by controlling composition
gradients--especially in instances when the insertion occurs in the early
stages of catalyst activation. In a solution loop reactor, for example, a
gradient of monomer composition can be achieved by modifying the speed at
which the reactor effluent circulates through the reactor. This can
result in differences in the comonomer mole fraction at different places
within the reactor. The reactor can be configured to take advantage of
this by strategic placement of catalyst and monomer injection points
and/or the timing of said catalyst and monomer contact.

[0042] In yet another alternative, one or more compounds can be
synthesized directly so that the desired ratio of ethylene-inserted
cation:α-olefin-inserted cation can be directly controlled.

General Processes of Using a Pre-Catalyst to Control Molecular Weight

[0043] As stated above, the Applicants have discovered a number of ways to
control the molecular weight distribution in the production of an
ethylene/α-olefin interpolymer composition. One process comprises:
[0044] (a) selecting at least one suitable pre-catalyst comprising at
least one metal-aryl or metal-hydrocarbyl bond, wherein each pre-catalyst
molecule is essentially the same as every other pre-catalyst molecule;
[0045] (b) contacting ethylene, at least one α-olefin, and said
suitable pre-catalyst; [0046] (c) selecting ethylene:alpha-olefin
concentration ratios sufficient to activate the pre-catalyst, and [0047]
(d) forming an ethylene/α-olefin interpolymer composition under
continuous reaction polymerization conditions; and, optionally, [0048]
(e) selecting a molecular weight split of the interpolymer as determined
by the mole fractions (f) of the two or more monomers, n, such that the
mole fraction of monomer m is defined as:

[0048] f m = [ Monomer m ] i = 1 n [ Monomer i ] .
##EQU00002##

to produce an ethylene/α-olefin interpolymer composition with a
controlled bimodal or multi-modal molecular weight distribution.

[0049] Another process comprises: [0050] (a) selecting at least one
suitable pre-catalyst comprising at least one metal-aryl or
metal-hydrocarbyl bond, wherein each pre-catalyst molecule is essentially
the same as every other pre-catalyst molecule; [0051] (b) contacting at
least one organic compound, and said suitable pre-catalyst; [0052] (c)
selecting at least one organic compound concentration sufficient to
activate the pre-catalyst, and [0053] (d) forming an
ethylene/α-olefin interpolymer composition under continuous
reaction polymerization conditions; and, optionally, [0054] (e) selecting
a molecular weight split of the interpolymer as determined by the
concentration of the one or more organic compound(s) to produce an
ethylene/α-olefin interpolymer composition with a controlled
bimodal or multi-modal molecular weight distribution. Suitable
Pre-catalyst Contact with (1) Ethylene and an α-olefin or (2)
Organic Compound

[0055] The suitable pre-catalysts may be selected from any of those
comprising at least one metal-aryl or metal-hydrocarbyl bond. The aryl
may be any molecule or ligand which has the ring structure characteristic
of, for example, phenyl, naphalenyl, phenanthrenyl, anthracenyl, etc. The
hydrocarbyl may be any molecule or ligand comprising hydrogen and carbon
such as benzyl. Additionally, a heteroatom such as nitrogen, oxygen, etc.
may be substituted for one or more carbon atoms of the aryl or
hydrocarbyl such that aryl includes heteroaryl and hydrocarbyl includes
heterohydrocarbyl. Similarly, one or more hydrogens on the aryl or
hydrocarbyl may be replaced with any substituent which does not
substantially interfere with the desired activity of the pre-catalyst.
Such substituents include, but are not limited to, substituted or
unsubstituted alkyl, halo, nitro, amino, alkoxy, aryl, aliphatic,
cycloaliphatic, hydroxy, and the like. Preferably each pre-catalyst
molecule is essentially the same as every other pre-catalyst molecule. By
this is meant that the chemical structures of the molecules are
substantially the same. Also preferable are those structures in which
ring strain is capable of being relieved from the metal-hydrocarbyl
ligand when contacted with ethylene or an α-olefin.

[0056] Particularly suitable pre-catalysts are selected from the group
consisting of hydrocarbylamine substituted heteroaryl compounds
corresponding to the formula:

##STR00003##

wherein: [0057] R11 is selected from alkyl, cycloalkyl,
heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives
thereof containing from 1 to 30 atoms not counting hydrogen or a divalent
derivative thereof; [0058] T1 is a divalent bridging group of from 1
to 41 atoms other than hydrogen, preferably 1 to 20 atoms atoms other
than hydrogen, and most preferably a mono- or di-C1-20 hydrocarbyl
substituted methylene or silane group; and [0059] R12 is a
C5-20 heteroaryl group containing Lewis base functionality,
especially a pyridin-2-yl- or substituted pyridin-2-yl group or a
divalent derivative thereof; [0060] M1 comprises hafnium or other
Group 4 metal; [0061] X1 is an anionic, neutral or dianionic ligand
group; [0062] x1 is a number from 0 to 5 indicating the number of
such X1 groups; and bonds, optional bonds and electron donative
interactions are represented by lines, dotted lines and arrows
respectively, or a mixture thereof, in contact with a suitable
co-catalyst.

[0063] The pre-catalyst and optional catalysts if desired are contacted
with either (1) ethylene and an α-olefin or (2) an organic compound
such as, for example, acetone or a mixture of ketones or (3) mixtures
thereof, in a manner and in amounts sufficient to activate the
pre-catalyst. One skilled in the art will recognize that a cocatalyst
such as the ones described below may be useful at this stage or a later
stage. The conditions will generally vary depending upon the polymer
desired and the equipment employed. However, one skilled in the art can
readily determine the suitable conditions using the instant
specification, background knowledge, the prior art, and routine
experimentation. Guidance is given in, for example, U.S. Pat. Nos.
6,960,635; 6,946,535; 6,943,215; 6,927,256; 6,919,407; and 6,906,160
which are incorporated herein by reference. One advantage of the instant
processes is that a single catalyst may be employed in a single reactor.

[0064] The ethylene, α-olefin, and/or organic compound
concentrations are typically selected so as to be sufficient to activate
the pre-catalyst, and form the desired ethylene/α-olefin
interpolymer composition having the desired molecular weight
distribution. These activation conditions vary depending on the reactants
and equipment employed and may be the same but are preferably different
than the continuous polymerization reaction conditions used to form the
interpolymer. More specifically, the initial monomer ratio used during
activation may be the same but is preferably different than the monomer
ratio used during the interpolymer polymerization. While these ratios
often vary according the reaction conditions and the product desired, the
molecular weight split of the interpolymer may usually be controlled by
selecting the mole fractions (f) of the two or more monomers, n, such
that the mole fraction of monomer m is defined as:

f m = [ Monomer m ] i = 1 n [ Monomer i ] .
##EQU00003##

[0065] Advantageously, the resulting polymer often has a low molecular
weight portion that has a higher density than the high molecular weight
portion. While batch or continuous polymerization reaction conditions may
be employed, it is preferable to employ continuous polymerization
reaction conditions during the formation of the interpolymer. However,
continuous polymerization reaction conditions can still be employed even
if the pre-catalyst is activated separately from the main polymerization.

General Processes of Using a Synthesized Catalyst to Control Molecular
Weight Distribution

[0066] Another process of controlling molecular weight comprises
contacting ethylene, an α-olefin, and a suitable catalyst under
reaction conditions sufficient to form an ethylene/α-olefin
interpolymer composition wherein the catalyst comprises a catalytic
amount of a molecule having the structure:

[0076] Use of various forms of the aforementioned catalyst structure
allows one skilled in the art to directly control the concentrations of
an "ethylene-inserted" form of the catalyst and an
"α-olefin-inserted" form of the catalyst. By directly controlling
these concentrations the molecular weight split of the interpolymer may
be controlled. This allows one skilled in the art to employ a much wider
range of reaction conditions yet still control the molecular weight
distribution. For example, it is then possible to control the molecular
weight distribution over a wider range of monomer concentrations.

[0077] The above catalyst may be synthesized by any convenient method.

[0092] As one skilled in the art can appreciate it may also be desirable
in some situations to use an in-situ synthesis method such that the
catalyst is formed during the polymerization reaction.

Cocatalysts

[0093] As one skilled in the art will appreciate it may be useful to
combine the pre-catalyst or synthesized catalyst with a suitable
cocatalyst, preferably a cation forming cocatalyst, a strong Lewis acid,
or a combination thereof. In a preferred embodiment, the shuttling agent,
if employed, is employed both for purposes of chain shuttling and as the
cocatalyst component of the catalyst composition.

[0094] The metal complexes desirably are rendered catalytically active by
combination with a cation forming cocatalyst, such as those previously
known in the art for use with Group 4 metal olefin polymerization
complexes. Suitable cation forming cocatalysts for use herein include
neutral Lewis acids, such as C1-30 hydrocarbyl substituted Group 13
compounds, especially tri(hydrocarbyl)aluminum or tri(hydrocarbyl)boron
compounds and halogenated (including perhalogenated) derivatives thereof,
having from 1 to 10 carbons in each hydrocarbyl or halogenated
hydrocarbyl group, more especially perfluorinated tri(aryl)boron
compounds, and most especially tris(pentafluoro-phenyl)borane;
nonpolymeric, compatible, noncoordinating, ion forming compounds
(including the use of such compounds under oxidizing conditions),
especially the use of ammonium-, phosphonium-, oxonium-, carbonium-,
silylium- or sulfonium-salts of compatible, noncoordinating anions, or
ferrocenium-, lead- or silver salts of compatible, noncoordinating
anions; and combinations of the foregoing cation forming cocatalysts and
techniques. The foregoing activating cocatalysts and activating
techniques have been previously taught with respect to different metal
complexes for olefin polymerizations in the following references: EP
Patent Publication No. 277,003; U.S. Pat. Nos. 5,153,157, 5,064,802,
5,321,106, 5,721,185, 5,350,723, 5,425,872, 5,625,087, 5,883,204,
5,919,983 and 5,783,512; and International Patent Publication Nos. WO
99/15534 and WO 99/42467, all of which are incorporated herein by
reference.

[0095] Combinations of neutral Lewis acids, especially the combination of
a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl
group and a halogenated tri(hydrocarbyl)boron compound having from 1 to
20 carbons in each hydrocarbyl group, especially
tris(pentafluorophenyl)borane, further combinations of such neutral Lewis
acid mixtures with a polymeric or oligomeric alumoxane, and combinations
of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane
with a polymeric or oligomeric alumoxane may be used as activating
cocatalysts. Preferred molar ratios of metal
complex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to 1:5:20,
more preferably from 1:1:1.5 to 1:5:10.

[0096] Suitable ion forming compounds useful as cocatalysts in one
embodiment of the present invention comprise a cation which is a Bronsted
acid capable of donating a proton, and a compatible, noncoordinating
anion, A.sup.-. used herein, the term "noncoordinating" means an anion or
substance which either does not coordinate to the Group 4 metal
containing precursor complex and the catalytic derivative derived there
from, or which is only weakly coordinated to such complexes thereby
remaining sufficiently labile to be displaced by a neutral Lewis base. A
noncoordinating anion specifically refers to an anion which when
functioning as a charge balancing anion in a cationic metal complex does
not transfer an anionic substituent or fragment thereof to said cation
thereby forming neutral complexes. "Compatible anions" are anions which
are not degraded to neutrality when the initially formed complex
decomposes and are noninterfering with desired subsequent polymerization
or other uses of the complex.

[0097] Preferred anions are those containing a single coordination complex
comprising a charge-bearing metal or metalloid core which anion is
capable of balancing the charge of the active catalyst species (the metal
cation) which may be formed when the two components are combined. Also,
said anion should be sufficiently labile to be displaced by olefinic,
diolefinic and acetylenically unsaturated compounds or other neutral
Lewis bases such as ethers or nitriles.

[0098] Suitable metals include, but are not limited to, aluminum, gold and
platinum. Suitable metalloids include, but are not limited to, boron,
phosphorus, and silicon. Compounds containing anions which comprise
coordination complexes containing a single metal or metalloid atom are,
of course, well known and many, particularly such compounds containing a
single boron atom in the anion portion, are available commercially.

[0099] Preferably such cocatalysts may be represented by the following
general formula:

(L*-H)g+ (A)g-

wherein: [0100] L* is a neutral Lewis base; [0101] (L*-H)+ is a
conjugate Bronsted acid of L*; [0102] Ag- is a noncoordinating,
compatible anion having a charge of g-, and [0103] g is an integer from 1
to 3.

[0104] More preferably Ag- corresponds to the formula:
[M'Q4].sup.-;

wherein: [0105] M' is boron or aluminum in the +3 formal oxidation
state; and [0106] Q independently each occurrence is selected from
hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide,
halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and
halo-substituted silylhydrocarbyl radicals (including perhalogenated
hydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenated
silylhydrocarbyl radicals), said Q having up to 20 carbons with the
proviso that in not more than one occurrence is Q halide. Examples of
suitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No.
5,296,433.

[0107] In a more preferred embodiment, d is one, that is, the counter ion
has a single negative charge and is A.sup.-. Activating cocatalysts
comprising boron which are particularly useful in the preparation of
catalysts of this invention may be represented by the following general
formula:

(L*-H)+(BQ4).sup.-;

wherein: [0108] L* is as previously defined; [0109] B is boron in a
formal oxidation state of 3; and [0110] Q is a hydrocarbyl-,
hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-,
or fluorinated silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with
the proviso that in not more than one occasion is Q hydrocarbyl.

[0111] Preferred Lewis base salts are ammonium salts, more preferably
trialkylammonium salts containing one or more C12-40 alkyl groups.
Most preferably, Q is each occurrence a fluorinated aryl group,
especially, a pentafluorophenyl group.

[0112] Illustrative, but not limiting, examples of boron compounds which
may be used as an activating cocatalyst in the preparation of the
improved catalysts of this invention are

[0146] Another suitable ion forming, activating cocatalyst comprises a
compound which is a salt of a carbenium ion and a noncoordinating,
compatible anion represented by the formula:

[C]+A.sup.

wherein: [0147] [C]+ is a C1-20 carbenium ion; and [0148]
A.sup.- is a noncoordinating, compatible anion having a charge of -1. A
preferred carbenium ion is the trityl cation, that is triphenylmethylium.

[0149] A further suitable ion forming, activating cocatalyst comprises a
compound which is a salt of a silylium ion and a noncoordinating,
compatible anion represented by the formula:

[0152] Certain complexes of alcohols, mercaptans, silanols, and oximes
with tris(pentafluorophenyl)borane are also effective catalyst activators
and may be used according to the present invention. Such cocatalysts are
disclosed in U.S. Pat. No. 5,296,433.

[0154] A class of cocatalysts comprising non-coordinating anions
generically referred to as expanded anions, further disclosed in U.S.
Pat. No. 6,395,671, may be suitably employed to activate the metal
complexes of the present invention for olefin polymerization. Generally,
these cocatalysts (illustrated by those having imidazolide, substituted
imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide,
or substituted benzimidazolide anions) may be depicted as follows:

##STR00009##

wherein: A*+ is a cation, especially a proton containing cation, and
preferably is a trihydrocarbyl ammonium cation containing one or two
C10-40 alkyl groups, especially a methyldi
(C14-20alkyl)ammonium cation,

[0155] Q3, independently each occurrence, is hydrogen or a halo,
hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl,
(including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms
not counting hydrogen, preferably C1-20 alkyl, and

[0156] Q2 is tris(pentafluorophenyl)borane or
tris(pentafluorophenyl)alumane).

[0182] Other activators include those described in PCT publication WO
98/07515 such as tris (2,2',2''-nonafluorobiphenyl)fluoroaluminate.
Combinations of activators are also contemplated by the invention, for
example, alumoxanes and ionizing activators in combinations, see for
example, EP-A-0 573120, PCT publications WO 94/07928 and WO 95/14044 and
U.S. Pat. Nos. 5,153,157 and 5,453,410. WO 98/09996 describes activating
catalyst compounds with perchlorates, periodates and iodates, including
their hydrates. WO 99/18135 describes the use of organoboroaluminum
activators. WO 03/10171 discloses catalyst activators that are adducts of
Bronsted acids with Lewis acids. Other activators or methods for
activating a catalyst compound are described in for example, U.S. Pat.
Nos. 5,849,852, 5,859,653, 5,869,723, EP-A-615981, and PCT publication WO
98/32775. All of the foregoing catalyst activators as well as any other
know activator for transition metal complex catalysts may be employed
alone or in combination according to the present invention, however, for
best results alumoxane containing cocatalysts are avoided.

[0183] The molar ratio of catalyst/cocatalyst employed preferably ranges
from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most
preferably from 1:1000 to 1:1. Alumoxane, when used by itself as an
activating cocatalyst, is employed in large quantity, generally at least
100 times the quantity of metal complex on a molar basis.
Tris(pentafluorophenyl)borane, where used as an activating cocatalyst is
employed in a molar ratio to the metal complex of from 0.5:1 to 10:1,
more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. The
remaining activating cocatalysts are generally employed in approximately
equimolar quantity with the metal complex.

Novel Compositions of the Present Invention

[0184] Advantageously, novel compositions of the present invention
comprise an ethylene/alpha-olefin interpolymer composition with a
multi-modal molecular weight distribution and one or more molecules
having a gram molecular weight equal to about ((the molecular weight of
an aryl or hydrocarbyl-ligand of a pre-catalyst)+28+14*X), wherein X
represents an integer from zero to 10, preferably zero to 8. The aryl or
hydrocarbyl ligand may be any of those described herein. The molecule may
be observed in the composition by extracting the interpolymer with a
solvent such as methylene chloride, adding another solvent such as an
alcohol, e.g. ethanol, and decanting. The decantate can then be analyzed
by any convenient analytical method such as gas chromatography coupled
with mass spectroscopy. Said composition may also contain ethylene, an
α-olefin, a reaction product or a mixture thereof.

[0185] Other novel compositions of the present invention include the
catalyst which may be synthesized as described above optionally mixed
with ethylene, an α-olefin, a reaction product or a mixture
thereof.

Ethylene/α-olefin Multi-Block Interpolymer Component(s)

[0186] The general processes described above may also be used to produce
an ethylene/α-olefin multi-block interpolymer such as those
describe in, for example, copending U.S. application Ser. No. 11/376,835
filed on Mar. 15, 2006 and PCT Publication No. WO 2005/090427, filed on
Mar. 17, 2005, which in turn claims priority to U.S. Provisional
Application No. 60/553,906, filed Mar. 17, 2004. For purposes of United
States patent practice, the contents of the aforementioned applications
are herein incorporated by reference in their entirety. If such a
multi-block polymer is desired then the processes described above will
also generally include a catalyst such as one comprising zinc which is
different than any pre-catalyst that may be employed. In addition, a
shuttling agent such as diethyl zinc or others described in PCT
Publication No. WO 2005/090427 may be employed. Such processes may result
in a polymer wherein the polymer has one or more of the following
characteristics:

[0187] (1) an average block index greater than zero and up to about 1.0
and a molecular weight distribution, Mw/Mn, greater than about 1.3; or

[0188] (2) at least one molecular fraction which elutes between 40°
C. and 130° C. when fractionated using TREF, characterized in that
the fraction has a block index of at least 0.5 and up to about 1; or

[0189] (3) an Mw/Mn from about 1.7 to about 3.5, at least one melting
point, Tm, in degrees Celsius, and a density, d, in grams/cubic
centimeter, wherein the numerical values of Tm and d correspond to the
relationship:

[0191] (4) an Mw/Mn from about 1.7 to about 3.5, and is characterized by a
heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in
degrees Celsius defined as the temperature difference between the tallest
DSC peak and the tallest CRYSTAF peak, wherein the numerical values of
ΔT and ΔH have the following relationships:

[0192] ΔT>-0.1299(ΔH)+62.81 for ΔH greater than zero
and up to 130 J/g,

[0193] ΔT≧48° C. for ΔH greater than 130 J/g,

[0194] wherein the CRYSTAF peak is determined using at least 5 percent of
the cumulative polymer, and if less than 5 percent of the polymer has an
identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.;
or

[0195] (5) an elastic recovery, Re, in percent at 300 percent strain and 1
cycle measured with a compression-molded film of the
ethylene/α-olefin interpolymer, and has a density, d, in
grams/cubic centimeter, wherein the numerical values of Re and d satisfy
the following relationship when ethylene/α-olefin interpolymer is
substantially free of a cross-linked phase:

[0196] Re>1481-1629(d); or

[0197] (6) a molecular fraction which elutes between 40° C. and
130° C. when fractionated using TREF, characterized in that the
fraction has a molar comonomer content of at least 5 percent higher than
that of a comparable random ethylene interpolymer fraction eluting
between the same temperatures, wherein said comparable random ethylene
interpolymer has the same comonomer(s) and has a melt index, density, and
molar comonomer content (based on the whole polymer) within 10 percent of
that of the ethylene/α-olefin interpolymer; or

[0198] (7) a storage modulus at 25° C., G'(25° C.), and a
storage modulus at 100° C., G'(100° C.), wherein the ratio
of G'(25° C.) to G'(100° C.) is in the range of about 1:1
to about 9:1; or

[0199] (8) has a DSC melting curve characterized by an area under the DSC
melting curve from the melting peak temperature to the end of melting is
at least about 17%, at least about 18%, at least about 19%, at least
about 21%, at least about 23%, at least about 25%, at least about 27%, at
least about 29%, at least about 31%, at least about 33%, to at most 25,
preferably 35% of the total area under the DSC melting curve from
-20° C. to the end of melting or

[0200] (9) has a B value of greater than about 0.98, greater than about
0.99, greater than about 1.0 or greater than about 1.02.

[0201] It has been found that when a cocatalyst shuttling agent, e.g.
diethyl zinc, is employed interpolymers having improved residual enthalpy
and hot tack are often made. In addition, it has also been observed that
the interpolymers may be manufactured to have little or no long chain
branching. When a shuttling agent is not employed, improved properties,
e.g., Dart impact, tear, puncture resistance may be observed.

[0202] The interpolymers of and used in the present invention preferably
have a density in the range of from about 0.875 g/cc to about 0.915 g/cc,
preferably from about 0.895 g/cc to about 0.910 g/cc; a molecular weight
distribution in the range from about 2.0 to about 3.8, from about 2.2 to
about 3.5, from about 2.2 to about 3.3, or from about 2.2 to about 3.8;
an I10/I2 in the range from about 5.5 to about 6.5, preferably
from about 5.6 to about 6.3; an I2 melt index in the range from
about 0.2 to about 20.

[0203] The B-values of the interpolymers of the present invention often
have a B value of greater than about 0.98, greater than about 0.99,
greater than about 1.0 or greater than about 1.02. "B-value" and similar
terms mean the ethylene units of an ethylene/α-olefin interpolymer
are distributed across the polymer chain in a nonrandom manner. B-values
range from 0 to 2. The higher the B-value, the more alternating the
comonomer distribution in the copolymer. The lower the B-value, the more
blocky or clustered the comonomer distribution in the copolymer.

[0204] There are several ways to calculate B-value; the method described
below utilizes the method of Koenig, J. L., where a B-value of 1
designates a perfectly random distribution of comonomer units. The
B-value as described by Koenig is calculated as follows. B is defined for
an ethylene/α-olefin interpolymer as an index of composition
distribution of constituent units derived from each monomer in the
interpolymer chain, and can be calculated from the following formula:

B = P EO 2 P O P E ##EQU00004##

[0205] wherein PE and PO are respectively a molar fraction of
the ethylene component and a molar fraction of the α-olefin (e.g.,
octene) component contained in the ethylene/α-olefin interpolymer
such as ethylene/octene interpolymer; and PEO is a molar fraction of
the ethylene/α-olefin chain such as ethylene/octene chain in all
the dyad chains.

[0206] In some embodiments, the values of PO, PB and PEO
for an ethylene/α-olefin interpolymer such as ethylene/octene
interpolymer can be obtained in the following manner. In a sample tube
having a diameter of 10 mm, about 200 mg of the ethylene/α-olefin
interpolymer is homogeneously dissolved in 1 ml of hexachlorobutadiene to
give a sample, and a 13C-NMR spectrum of the sample is measured
according to literature references, such as G. J. Ray (Macromolecules,
10, 773, 1977) and J. C. Randall (Macromolecules, 15, 353, 1982; J.
Polymer Science, Polymer Physics Ed., 11, 275, 1973), and K. Kimura
(Polymer, 25, 441, 1984). B values are also discussed in the publication
WO 2006/069205 A1 published Jun. 29, 2006 and incorporated herein by
reference. The B value is 2 when the ethylene/α-olefin interpolymer
such as ethylene/octene interpolymer is a perfectly alternating
interpolymer, while the B value is 0 when the interpolymer is a perfectly
block interpolymer.

[0207] The ethylene/α-olefin interpolymers of the present invention,
e.g. ethylene-octene, advantageously can be made using less
α-olefin, e.g. octene, than prior polymers yet the interpolymers of
the present invention have approximately the same or higher density. This
is shown in, for example, FIG. 29 which shows that the
ethylene/α-olefin interpolymers of the present invention often
comprise one or more of the following characteristics: a density in g/cc,
d, and a weight percent α-olefin, Wt. %, wherein the numerical
values of d and Wt. % correspond to the relationship: d≦-0.0018
Wt. %+0.9297 and/or d≦-0.0019 Wt. %+0.933. This is a surprising
and unexpected relationship in that typically the density will decrease
more with decreasing amounts of α-olefin. It has been discovered
that the use of a shuttling agent may affect the aforementioned
relationships. For example, the interpolymers made with a shuttling agent
such as diethyl zinc often exhibit the relationship: d≦-0.0018 Wt.
%+0.9297 whereas interpolymers made without a shuttling agent such as
diethyl zinc often exhibit the relationship: d≦-0.0019 Wt.
%+0.933. FIG. 29 is a plot showing the density of an
ethylene/α-olefin interpolymer as a function of the weight
percentage of 1-octene for inventive polymers made using diethyl zinc
(DEZ) and inventive polymers made without using DEZ.

Applications and End Uses

[0208] The polymers of the present invention can be used in a variety of
conventional thermoplastic fabrication processes to produce useful
articles. Such articles include objects comprising at least one film
layer, such as a monolayer film, or at least one layer in a multilayer
film prepared by cast, blown, calendered, or extrusion coating processes;
molded articles, such as blow molded, injection molded, or rotomolded
articles; extrusions; fibers; and woven or non-woven fabrics.

[0209] Due to the surprising and unexpected hot tack properties, as well
as, the puncture and Dart impact properties the polymers and compositions
of the present invention are particularly suited for food applications
such as form, fill and seal applications. Film layers of the present
invention may often be made wherein the average hot tack (ASTM F 1921,
Method B, dwell time of 500 ms, seal pressure of 27.5 N/cm2) is at
least 10 N over a temperature range of at least 20° C., preferably
25° C., more preferably 28° C. Heat sealable films made
with the composition of the present invention may be employed in either
monolayer or multilayer film structures or as laminates. Regardless of
how the film is utilized, it may be prepared by a variety of processes
that are well known to those of skill in the art.

[0210] Film structures may be made by conventional fabrication techniques,
e.g. simple bubble extrusion, biaxial orientation processes (such as
tenter frames or double bubble processes), simple cast/sheet extrusion,
coextrusion, lamination, etc. Conventional simple bubble extrusion
processes (also known as hot blown film processes) are described, for
example, in The Encyclopedia of Chemical Technology, Kirk-Othmer, Third
Edition, John Wiley & Sons, New York, 1981, Vol. 16, pp. 416-417 and Vol.
18, pp. 191-192, the disclosures of which are incorporated herein by
reference. Biaxial orientation film manufacturing processes such as
described in the "double bubble" process of U.S. Pat. No. 3,456,044
(Pahlke), and the processes described in U.S. Pat. No. 4,352,849
(Mueller), U.S. Pat. Nos. 4,820,557 and 4,837,084 (both to Warren), U.S.
Pat. No. 4,865,902 (Golike et al.), U.S. Pat. No. 4,927,708 (Herran et
al.), U.S. Pat. No. 4,952,451 (Mueller), and U.S. Pat. Nos. 4,963,419 and
5,059,481 (both to Lustig et al.), the disclosures of which are
incorporated herein by reference, can also be used to make the novel film
structures of this invention. Biaxially oriented film structures can also
be made by a tenter-frame technique, such as that used for oriented
polypropylene.

[0211] Other multilayer film manufacturing techniques for food packaging
applications are described in Packaging Foods With Plastics by Wilmer A.
Jenkins and James P. Harrington (1991), pp. 19-27, and in "Coextrusion
Basics" by Thomas I. Butler, Film Extrusion Manual: Process, Materials,
Properties. pp. 31-80 (published by TAPPI Press (1992)) the disclosures
of which are incorporated herein by reference.

[0212] In certain embodiments of this invention, at least one heat
sealable, innermost or outermost layer (i.e., sealing or skin layer) of a
film structure comprises the polymers of the present invention. This heat
sealable layer can be coextruded with other layer(s) or the heat sealable
layer can be laminated onto another layer(s) or substrate in a secondary
operation, such as that described in Packaging Foods With Plastics, ibid,
or that described in "Coextrusion For Barrier Packaging" by W. J. Schrenk
and C. R. Finch, Society of Plastics Engineers RETEC Proceedings Jun.
15-17, 1981, pp. 211-229, the disclosures of which are incorporated
herein by reference. Preferable substrates include papers, foils,
oriented polypropylenes, polyamides, polyesters, polyethylenes,
polyethylene terephthalate, and, metallized substrates.

[0213] Should a multilayer film be desired, such may be obtained from a
monolayer film which has been previously produced via tubular film (i.e.,
blown film techniques) or flat die (i.e. cast film) as described by K. R.
Osborn and W. A. Jenkins in "Plastic Films, Technology and Packaging
Applications" (Technomic Publishing Co., Inc. (1992)), the disclosures of
which are incorporated herein by reference, wherein the sealant film must
go through an additional post-extrusion step of adhesive or extrusion
lamination to other packaging material layers. If the sealant film is a
coextrusion of two or more layers (also described by Osborn and Jenkins),
the film may still be laminated to additional layers of packaging
materials, depending on the other physical requirements of the final
packaging film. "Laminations vs. Coextrusions" by D. Dumbleton
(Converting Magazine, September 1992), the disclosure of which is
incorporated herein by reference, also discusses lamination versus
coextrusion. Monolayer and coextruded films can also go through other
post-extrusion techniques, such as a biaxial orientation process and
irradiation. With respect to irradiation, this technique can also precede
extrusion by irradiating the pellets from which the film is to be
fabricated prior to feeding the pellets into the extruder, which
increases the melt tension of the extruded polymer film and enhances
processability.

[0214] Extrusion coating is yet another technique for producing packaging
materials. Similar to cast film, extrusion coating is a flat die
technique. A heat-sealable film comprised of the compositions of the
present invention can be extrusion coated onto a substrate either in the
form of a monolayer or a coextruded extrudate according to, for example,
the processes described in U.S. Pat. No. 4,339,507 incorporated herein by
reference. Utilizing multiple extruders or by passing the various
substrates through the extrusion coating system several times can result
in multiple polymer layers each providing some sort of performance
attribute whether it be barrier, toughness, or improved hot tack or heat
sealability. Some typical end use applications for
multi-layered/multi-substrate systems are for cheese packages. Other end
use applications include, but are not limited to moist pet foods, snacks,
chips, frozen foods, meats, hot dogs, and numerous other applications.

[0215] In those embodiments in which the film comprises one or more of the
polymers of the present invention, other layers of the multilayer
structure may be included to provide a variety of performance attributes.
These layers can be constructed from various materials, including blends
of homogeneous linear or substantially linear ethylene polymers with
polypropylene polymers, and some layers can be constructed of the same
materials, e.g some films can have the structure A/B/C/B/A wherein each
different letter represents a different composition. Representative,
nonlimiting examples of materials in other layers are: poly(ethylene
terephthalate) (PET), ethylene/vinyl acetate (EVA) copolymers,
ethylene/acrylic acid (BAA) copolymers, ethylene/methacrylic acid (EMAA)
copolymers, LLDPE, HDPE, LDPE, graft-modified ethylene polymers (e.g
maleic anhydride grafted polyethylene), styrene-butadiene polymers (such
as K-resins, available from Phillips Petroleum), etc. Generally,
multilayer film structures comprise from 2 to about 7 layers.

[0216] The thickness of the multilayer structures is typically from about
1 mil to about 4 mils (total thickness). The heat sealable film layer
varies in thickness depending on whether it is produced via coextrusion
or lamination of a monolayer or coextruded film to other packaging
materials. In a coextrusion, the heat sealable film layer is typically
from about 0.1 to about 3 mils, preferably from about 0.4 to about 2
mils. In a laminated structure, the monolayer or coextruded heat sealable
film layer is typically from about 0.5 to about 2 mils, preferably from
about 1 to 2 mils. For a monolayer film, the thickness is typically
between about 0.4 mil to about 4 mils, preferably between about 0.8 to
about 2.5 mils.

[0217] The heat sealable films of the invention can be made into packaging
structures such as form-fill-seal structures or bag-in-box structures.
For example, one such form-fill-seal operation is described in Packaging
Foods With Plastics, ibid, pp. 78-83. Packages can also be formed from
multilayer packaging roll stock by vertical or horizontal form-fill-seal
packaging and thermoform-fill-seal packaging, as described in "Packaging
Machinery Operations: No. 8, Form-Fill-Sealing, A Self-Instructional
Course" by C. G. Davis, Packaging Machinery Manufacturers Institute
(April 1982); The Wiley Encyclopedia of Packaging Technology by M. Bakker
(Editor), John Wiley & Sons (1986), pp. 334, 364-369; and Packaging: An
Introduction by S. Sacharow and A. L. Brody, Harcourt Brace Javanovich
Publications, Inc. (1987), pp. 322-326. The disclosures of all of the
preceding publications are incorporated herein by reference. A
particularly useful device for form-fill-seal operations is the Hayssen
Ultima Super CMB Vertical Form-Fill-Seal Machine. Other manufacturers of
pouch thermoforming and evacuating equipment include Cryovac and Koch. A
process for making a pouch with a vertical form-fill-seal machine is
described generally in U.S. Pat. Nos. 4,503,102 and 4,521,437, both of
which are incorporated herein by reference. Film structures containing
one or more layers comprising a heat sealable film of the present
invention are well suited for the packaging of potable water, wine,
cheese, potatoes, condiments, and similar food products in such
form-fill-seal structures.

[0218] The films of the invention can be cross-linked, before or after
orientation, by any means known in the art, including, but not limited
to, electron-beam irradiation, beta irradiation, gamma irradiation,
corona irradiation, silanes, peroxides, allyl compounds and UV radiation
with or without crosslinking catalyst. U.S. Pat. Nos. 6,803,014 and
6,667,351 disclose electron-beam irradiation methods that can be used in
embodiments of the invention.

[0219] Irradiation may be accomplished by the use of high energy, ionizing
electrons, ultra violet rays, X-rays, gamma rays, beta particles and the
like and combination thereof. Preferably, electrons are employed up to 70
megarads dosages. The irradiation source can be any electron beam
generator operating in a range of about 150 kilovolts to about 6
megavolts with a power output capable of supplying the desired dosage.
The voltage can be adjusted to appropriate levels which may be, for
example, 100,000, 300,000, 1,000,000 or 2,000,000 or 3,000,000 or
6,000,000 or higher or lower. Many other apparati for irradiating
polymeric materials are known in the art. The irradiation is usually
carried out at a dosage between about 3 megarads to about 35 megarads,
preferably between about 8 to about 20 megarads. Further, the irradiation
can be carried out conveniently at room temperature, although higher and
lower temperatures, for example 0° C. to about 60° C., may
also be employed. Preferably, the irradiation is carried out after
shaping or fabrication of the article, such as a film. Also, in a
preferred embodiment, the ethylene interpolymer which has been
incorporated with a pro-rad additive is irradiated with electron beam
radiation at about 8 to about 20 megarads.

[0220] Crosslinking can be promoted with a crosslinking catalyst, and any
catalyst that will provide this function can be used. Suitable catalysts
generally include organic bases, carboxylic acids, and organometallic
compounds including organic titanates and complexes or carboxylates of
lead, cobalt, iron, nickel, zinc and tin. Dibutyltindilaurate,
dioctyltinmaleate, dibutyltindiacetate, dibutyltindioctoate, stannous
acetate, stannous octoate, lead naphthenate, zinc caprylate, cobalt
naphthenate; and the like. Tin carboxylate, especially
dibutyltindilaurate and dioctyltinmaleate, are particularly effective.
The catalyst (or mixture of catalysts) is present in a catalytic amount,
typically between about 0.015 and about 0.035 phr.

[0222] At least one pro-rad additive can be introduced to the ethylene
interpolymer by any method known in the art. However, preferably the
pro-rad additive(s) is introduced via a masterbatch concentrate
comprising the same or different base resin as the ethylene interpolymer.
Preferably, the pro-rad additive concentration for the masterbatch is
relatively high e.g., about 25 weight percent (based on the total weight
of the concentrate).

[0223] The at least one pro-rad additive is introduced to the ethylene
polymer in any effective amount. Preferably, the at least one pro-rad
additive introduction amount is from about 0.001 to about 5 weight
percent, more preferably from about 0.005 to about 2.5 weight percent and
most preferably from about 0.015 to about 1 weight percent (based on the
total weight of the ethylene interpolymer.

[0224] In addition to electron-beam irradiation, crosslinking can also be
effected by UV irradiation. U.S. Pat. No. 6,709,742 discloses a
cross-linking method by UV irradiation which can be used in embodiments
of the invention. The method comprises mixing a photoinitiator, with or
without a photocrosslinker, with a polymer before, during, or after a
fiber is formed and then exposing the fiber with the photoinitiator to
sufficient UV radiation to crosslink the polymer to the desired level.
The photoinitiators used in the practice of the invention are aromatic
ketones, e.g., benzophenones or monoacetals of 1,2-diketones. The primary
photoreaction of the monacetals is the homolytic cleavage of the a-bond
to give acyl and dialkoxyalkyl radicals. This type of a-cleavage is known
as a Norrish Type I reaction which is more fully described in W. Horspool
and D. Armesto, Organic Photochemistry: A Comprehensive Treatment, Ellis
Horwood Limited, Chichester, England, 1992; J. Kopecky, Organic
Photochemistry: A Visual Approach, VCH Publishers, Inc., New York, N.Y.
1992; N.J. Turro, et al., Acc. Chem. Res., 1972, 5, 92; and J. T. Banks,
et al., J. Am. Chem. Soc., 1993, 115, 2473. The synthesis of monoacetals
of aromatic 1,2 diketones, Ar--CO--C(OR)2--Ar' is described in U.S.
Pat. No. 4,190,602 and Ger. Offen. 2,337,813. The preferred compound from
this class is 2,2-dimethoxy-2-phenylacetophenone,
C6H5--CO--C(OCH3)2--C6H5, which is
commercially available from Ciba-Geigy as Irgacure 651. Examples of other
aromatic ketones useful as photoinitiators are Irgacure 184, 369, 819,
907 and 2959, all available from Ciba-Geigy.

[0225] In one embodiment of the invention, the photoinitiator is used in
combination with a photocrosslinker. Any photocrosslinker that will upon
the generation of free radicals, link two or more olefin polymer
backbones together through the formation of covalent bonds with the
backbones can be used. Preferably these photocrosslinkers are
polyfunctional, i.e., they comprise two or more sites that upon
activation will form a covalent bond with a site on the backbone of the
copolymer. Representative photocrosslinkers include, but are not limited
to polyfunctional vinyl or allyl compounds such as, for example,.
triallyl cyanurate, triallyl isocyanurate, pentaerthritol
tetramethacrylate, ethylene glycol dimethacrylate, diallyl maleate,
dipropargyl maleate, dipropargyl monoallyl cyanurate and the like.
Preferred photocrosslinkers for use in some embodiments of the invention
are compounds which have polyfunctional (i.e. at least two) moieties.
Particularly preferred photocrosslinkers are triallycyanurate (TAC) and
triallylisocyanurate (TAIC).

[0226] Certain compounds act as both a photoinitiator and a
photocrosslinker. These compounds are characterized by the ability to
generate two or more reactive species (e.g., free radicals, carbenes,
nitrenes, etc.) upon exposure to UV-light and to subsequently covalently
bond with two polymer chains. Any compound that can preform these two
functions can be used in some embodiments of the invention, and
representative compounds include the sulfonyl azides described in U.S.
Pat. Nos. 6,211,302 and 6,284,842.

[0227] In another embodiment of this invention, the copolymer is subjected
to secondary crosslinking, i.e., crosslinking other than and in addition
to photocrosslinking. In this embodiment, the photoinitiator is used
either in combination with a nonphotocrosslinker, e.g., a silane, or the
copolymer is subjected to a secondary crosslinking procedure, e.g,
exposure to E-beam radiation. Representative examples of silane
crosslinkers are described in U.S. Pat. No. 5,824,718, and crosslinking
through exposure to E-beam radiation is described in U.S. Pat. Nos.
5,525,257 and 5,324,576. The use of a photocrosslinker in this embodiment
is optional.

[0228] At least one photoadditive, i.e., photoinitiator and optional
photocrosslinker, can be introduced to the copolymer by any method known
in the art. However, preferably the photoadditive(s) is (are) introduced
via a masterbatch concentrate comprising the same or different base resin
as the copolymer. Preferably, the photoadditive concentration for the
masterbatch is relatively high e.g., about 25 weight percent (based on
the total weight of the concentrate).

[0229] The at least one photoadditive is introduced to the copolymer in
any effective amount. Preferably, the at least one photoadditive
introduction amount is from about 0.001 to about 5, more preferably from
about 0.005 to about 2.5 and most preferably from about 0.015 to about 1,
wt % (based on the total weight of the copolymer).

[0230] The photoinitiator(s) and optional photocrosslinker(s) can be added
during different stages of the film manufacturing process. If
photoadditives can withstand the extrusion temperature, an olefin polymer
resin can be mixed with additives before being fed into the extruder,
e.g., via a masterbatch addition. Alternatively, additives can be
introduced into the extruder just prior the slot die, but in this case
the efficient mixing of components before extrusion is important. In
another approach, olefin polymer films can be oriented without
photoadditives, and a photoinitiator and/or photocrosslinker can be
applied to the extruded film via a kiss-roll, spray, dipping into a
solution with additives, or by using other industrial methods for
post-treatment. The resulting film with photoadditive(s) is then cured
via electromagnetic radiation in a continuous or batch process. The photo
additives can be blended with an olefin polymer using conventional
compounding equipment, including single and twin-screw extruders.

[0231] The power of the electromagnetic radiation and the irradiation time
are chosen so as to allow efficient crosslinking without polymer
degradation and/or dimensional defects. The preferred process is
described in EP 0 490 854 B1. Photoadditive(s) with sufficient thermal
stability is (are) premixed with an olefin polymer resin, extruded into a
film, and irradiated in a continuous process using one energy source or
several units linked in a series. There are several advantages to using a
continuous process compared with a batch process to cure a film.

[0232] Irradiation may be accomplished by the use of UV-radiation.
Preferably, UV-radiation is employed up to the intensity of 100
J/cm2. The irradiation source can be any UV-light generator
operating in a range of about 50 watts to about 25000 watts with a power
output capable of supplying the desired dosage. The wattage can be
adjusted to appropriate levels which may be, for example, 1000 watts or
4800 watts or 6000 watts or higher or lower. Many other apparati for
UV-irradiating polymeric materials are known in the art. The irradiation
is usually carried out at a dosage between about 3 J/cm2 to about
500 J/scm2,, preferably between about 5 J/cm2 to about 100
J/cm2. Further, the irradiation can be carried out conveniently at
room temperature, although higher and lower temperatures, for example
0° C. to about 60° C., may also be employed. The
photocrosslinking process is faster at higher temperatures. Preferably,
the irradiation is carried out after shaping or fabrication of the
article. In a preferred embodiment, the copolymer which has been
incorporated with a photoadditive is irradiated with UV-radiation at
about 10 J/cm2 to about 50 J/cm2.

[0233] The polymers described herein are also useful for wire and cable
coating operations, as well as in sheet extrusion for vacuum forming
operations, and forming molded articles, including the use of injection
molding, blow molding process, or rotomolding processes. Compositions
comprising the olefin polymers can also be formed into fabricated
articles such as those previously mentioned using conventional polyolefin
processing techniques which are well known to those skilled in the art of
polyolefin processing. Dispersions, both aqueous and non-aqueous, can
also be formed using the polymers or formulations comprising the same.
Frothed foams comprising the invented polymers can also be formed, as
disclosed in PCT application No. PCT/US2004/027593, filed Aug. 25, 2004,
and published as WO2005/021622. The polymers may also be crosslinked by
any known means, such as the use of peroxide, electron beam, silane,
azide, or other cross-linking technique. The polymers can also be
chemically modified, such as by grafting (for example by use of maleic
anhydride (MAH), silanes, or other grafting agent), halogenation,
amination, sulfonation, or other chemical modification.

[0235] As stated above, the bimodal molecular weight "split" of the
polymer may be selected by controlling the mole fractions (f) of the two
or more monomers, n, such that the mole fraction of monomer m is defined
as:

f m = [ Momomer m ] i = 1 n [ Monomer i ] .
##EQU00005##

[0236] This may be quantified for an ethylene-octene copolymer as depicted
in FIGS. 20 and 21. At low f2, the low molecular weight fraction
predominates, but at higher f2, the higher molecular weight species
is more prevalent.

General Experimental Considerations

[0237] Unless specified otherwise, all reagents are handled under
anaerobic conditions using standard procedures for the handling of
extremely air- and water-sensitive materials. Solvents are used without
further purification. All other chemicals are commercial materials and
are used as received.

General Reactor Polymerization Procedure

[0238] A one-gallon AE autoclave is purged at high temperature with
N2. ISOPAR® E was added, and the reactor is heated to
120° C. 1-Octene and hydrogen are added batchwise to the reactor
and are not regulated during the run. The reactor is then pressurized
with ethylene (450 psi). Solutions of the pre-catalyst, cocatalyst (1.2
equivalents to pre-catalyst), and a scavenger (5 equivalents to
pre-catalyst) are mixed and then added to the reactor using a flush of
high pressure ISOPAR® E. Polymer yield is kept low to minimize
monomer composition drift during the experiment. After the prescribed
reaction time, reactor contents are dumped into a resin kettle and mixed
with IRGANOX® 1010/IRGAFOS® 168 stabilizer mixture (1 g). The
polymer is recovered by evaporating the majority of the solvent at room
temperature and then dried further in a vacuum oven overnight at
90° C. Following the run, the reactor is hot-flushed with
ISOPAR® E to prevent polymer contamination from run to run.

[0239] Continuous solution polymerizations are carried out in a computer
controlled autoclave reactor equipped with an internal stirrer. Purified
mixed alkanes solvent (ISOPAR® E available from ExxonMobil, Inc.),
ethylene, 1-octene, and hydrogen (where used) are supplied to a reactor
equipped with a jacket for temperature control and an internal
thermocouple. The solvent feed to the reactor is measured by a mass-flow
controller. A variable speed diaphragm pump controls the solvent flow
rate and pressure to the reactor. At the discharge of the pump, a side
stream is taken to provide flush flows for the catalyst and cocatalyst 1
injection lines and the reactor agitator. These flows are measured by
Micro-Motion mass flow meters and controlled by control valves or by the
manual adjustment of needle valves. The remaining solvent is combined
with 1-octene, ethylene, and hydrogen (where used) and fed to the
reactor. A mass flow controller is used to deliver hydrogen to the
reactor as needed. The temperature of the solvent/monomer solution is
controlled by use of a heat exchanger before entering the reactor. This
stream enters the bottom of the reactor. The catalyst component solutions
are metered using pumps and mass flow meters and are combined with the
catalyst flush solvent and introduced into the bottom of the reactor. The
reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.
Product is removed through exit lines at the top of the reactor. All exit
lines from the reactor are steam traced and insulated. Polymerization is
stopped by the addition of a small amount of water into the exit line
along with any stabilizers or other additives and passing the mixture
through a static mixer. The product stream is then heated by passing
through a heat exchanger before devolatilization. The polymer product is
recovered by extrusion using a devolatilizing extruder and water cooled
pelletizer. Process details and results are contained in Table 2.
Selected polymer properties are provided in Table 3.

[0242] Examples 16-22 were prepared in manner similar to the procedure
described for Examples 12-15 except that the process parameters of Table
4 below were employed. The properties of the resulting polymers of
Examples 16-22 are shown in Tables 5 and 6 below.

[0243] The Differential Scanning Calorimetry (DSC) curves of Examples
16-21 and Comparative Examples A-F were measured according to the
procedure below. A TA Instruments model Q1000 DSC equipped with an RCS
cooling accessory and an autosampler was used. A nitrogen purge gas flow
of 50 ml/minute was used. The sample was pressed and melted in a press at
about 175° C. and then air-cooled to room temperature (25°
C.) to form a thin film. A disk of about 4-8 mg and 6 mm in diameter was
cut from the thin film, accurately weighed, placed in a light aluminum
pan (ca 50 mg), and then crimped shut. Thermal behavior of the sample was
investigated with the following temperature profile. The sample was
rapidly heated to 180° C. and held isothermal for 3 minutes in
order to remove any previous thermal history. The sample was then cooled
to -40° C. at 10° C/minute cooling rate and held at
-40° C. for 3 minutes. The sample was then heated to 190°
C. at 10° C./minute heating rate. The area under the melting curve
was measured from -20° C. to the end of the melting. The DSC
curves of Examples 16, 17, 20, and 21 are shown in FIGS. 22, 23, 24 and
25 respectively. The DSC curve of Example 22 is shown in FIG. 28. The
melting peak temperature is chosen as the temperature at the maximum in
heat flow with respect to a linear baseline. For example, the melting
peak temperature for Example 17 shown in FIG. 23 is 99.28° C., not
122.07° C. The melting peak temperatures are reported in Table 6
below. The area under the DSC curve from the melting peak temperature to
the end of the melting is reported as the melting peak residual area.
Similarly, the enthalpy corresponding to the melting peak residual area
is the residual enthalpy at melting peak. The melting peak residual area
as a percentage of the total enthalpy or heat of fusion is also reported.
The DSC results are listed in Table 6 below.

[0244] Two DSC curves for Comparative Polymer A were run using different
DSC instruments. FIGS. 26 and 27 show DSC curves of Comparative Polymer A
obtained using a TA Instruments model Q1000 DSC and a TA Instruments
model 2920 DSC respectively. The DSC curves of Examples 16 and 17 are
bimodal and broader than that of Comparative Polymer A.

Long Chain Branching (LCB)

[0245] The LCB results shown in Table 7 may be obtained using the
techniques described in, for example, Randall (Rev. Macromol. Chem.
Phys., C29 (2&3), p. 285-297), the disclosure of which is incorporated
herein by reference, or the techniques described by A. Willem deGroot and
P. Steve Chum Oct. 4, 1994 conference of the Federation of Analytical
Chemistry and Spectroscopy Society (FACSS) in St. Louis, Mo., U.S.A., the
disclosure of which is incorporated herein by reference.

[0246] The inventive interpolymers disclosed herein can be used in any
multilayer film known to a skilled artisan. In some embodiments, the
multilayer film comprises a base layer and a sealant layer. In other
embodiments, the multilayer film comprises a base layer, a sealant layer,
and a tie layer between the base layer and the sealant layer.

[0247] In some embodiments, the base layer is a heat resistant layer
having a melting point higher than that of the sealant layer. The heat
resistant layer can comprise a single polymer or a blend of two or more
polymers. Some non-limiting examples of suitable polymers for the heat
resistant layer include polyethylene, polypropylene, polybutadiene,
polystyrene, polyesters, polycarbonates, polyamides and combinations
thereof. Any other polymer that has a melting point higher than that of
the sealant layer disclosed herein can also be used. In a further
embodiment, the base layer comprises a polyamide.

[0248] In certain embodiments, the base layer is a non-heat resistant
layer having a melting point lower than that of the sealant layer. The
non-heat resistant layer can comprise a single polymer or a blend of two
more polymers. Some non-limiting examples of suitable polymers for the
non-heat resistant layer include low-density polyethylene, polypropylene,
poly(3-hydroxybutyrate) (PHB), polydimethylsiloxane and combinations
thereof. Any other polymer that has a melting point lower than that of
the sealant layer disclosed herein can also be used. In further
embodiments, the base layer has about the same melting point as the
sealant layer and comprises any of the polymers mentioned above or a
combination thereof.

[0249] In some embodiments, the thickness of the base layer can be from
about 1% to about 90%, from about 3% to about 80%, from about 5% to about
70%, from about 10% to about 60%, from about 15% to about 50%, or from
about 20% to about 40% of the total thickness of the multilayer film. In
other embodiments, the thickness of the base layer is from about 10% to
about 40%, from about 15% to about 35%, from about 20% to about 30%, or
from about 22.5% to about 27.5% of the total thickness of the multilayer
film. In further embodiments, the total thickness of the base layer is
about 25% of the total thickness of the multilayer film.

[0250] The sealant layer may comprise at least an ethylene/α-olefin
interpolymer disclosed herein. In some embodiments, the sealant layer may
further comprise one or more polymers comprising repeating units derived
from ethylene, for example, low density polyethylene, other
ethylene/α-olefin copolymers, ethylene/vinyl acetate copolymers,
ethylene/alkyl acrylate copolymers, ethylene/acrylic acid copolymers, as
well as the metal salts of ethylene/acrylic acid, commonly referred to as
inomers.

[0251] In some embodiments, the thickness of the sealant layer is from
about 1% to about 90%, from about 3% to about 80%, from about 5% to about
70%, from about 10% to about 60%, from about 15% to about 50%, or from
about 20% to about 40% of the total thickness of multilayer film. In
other embodiments, the thickness of the sealant layer is from about 10%
to about 40%, from about 15% to about 35%, from about 20% to about 30%,
or from about 22.5% to about 27.5% of the total thickness of the
multilayer film. In further embodiments, the total thickness of the
sealant layer is about 25% of the total thickness of the multi layer
film.

[0252] The tie layer can be any layer that can promote the adhesion
between its two adjacent layers. In some embodiments, the tie layer is
between or adjacent to the base layer and the sealant layer. Some
non-limiting examples of suitable polymers for the tie layer include
ethylene/vinyl acetate copolymers, ethylene/methyl acrylate copolymers,
ethylene/butyl acrylate copolymers, very low density polyethylene
(VLDPE), ultralow density polyethylene (ULDPE), TAFMER® resins, as
well as metallocene catalyzed ethylene/α-olefin copolymers of lower
densities. Generally, some resins suitable for use in the sealant layer
can serve as tie layer resins. In some embodiments, the thickness of the
sealant layer is from about 1% to about 99%, from about 10% to about 90%,
from about 20% to about 80%, from about 30% to about 70%, or from about
40% to about 60% of the total thickness of multilayer film. In other
embodiments, the thickness of the sealant layer is from about 45% to
about 55% of the total thickness of the multilayer film. In further
embodiments, the total thickness of the sealant layer is about 50% of the
total thickness of the multilayer film.

[0253] In some embodiments, the multilayer film comprises at least two
layers. For example, the multilayer film may comprise 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15 or more layers of films.

[0254] Optionally, each layer of the multilayer film, such as the base
layer, tie layer and sealant layer, may independently comprise or be
substantially free of at least an additive. Some non-limiting example of
suitable additive include plasticizers, oils, waxes, antioxidants, UV
stabilizers, colorants or pigments, fillers, flow aids, coupling agents,
crosslinking agents, surfactants, solvents, slip agents, anti-blocking
agents, lubricants, antifogging agents, nucleating agents, flame
retardants, antistatic agents and combinations thereof. The total amount
of the additives can range from about greater than 0 to about 80%, from
about 0.001% to about 70%, from about 0.01% to about 60%, from about 0.1%
to about 50%, from about 1% to about 40%, or from about 10% to about 50%
of the total weight of the multilayer film. Some polymer additives have
been described in Zweifel Hans et al., "Plastics Additives Handbook,"
Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001), which
is incorporated herein by reference in its entirety. In some embodiments,
the multilayer films disclosed herein do not comprise an additive such as
those disclosed herein.

[0255] In some embodiments, one or more layers of the multilayer film
optionally comprise a slip agent. Slip is the sliding of film surfaces
over each other or over some other substrates. The slip performance of
films can be measured by ASTM D 1894, Static and Kinetic Coefficients of
Friction of Plastic Film and Sheeting, which is incorporated herein by
reference. In general, the slip agent can convey slip properties by
modifying the surface properties of films; and reducing the friction
between layers of the films and between the films and other surfaces with
which they come into contact.

[0256] Any slip agent known to a person of ordinary skill in the art may
be added to at least an outer layer of the multilayer film disclosed
herein. Non-limiting examples of the slip agents include primary amides
having about 12 to about 40 carbon atoms (e.g., erucamide, oleamide,
stearamide and behenamide); secondary amides having about 18 to about 80
carbon atoms (e.g., stearyl erucamide, behenyl erucamide, methyl
erucamide and ethyl erucamide); secondary-bis-amides having about 18 to
about 80 carbon atoms (e.g., ethylene-bis-stearamide and
ethylene-bis-oleamide); and combinations thereof.

[0257] Optionally, one or more layers of the multilayer film disclosed
herein can comprise an anti-blocking agent. In some embodiments, the
multilayer film disclosed herein do not comprise an anti-blocking agent.
The anti-blocking agent can be used to prevent the undesirable adhesion
between touching layers of the multilayer film, particularly under
moderate pressure and heat during storage, manufacture or use. Any
anti-blocking agent known to a person of ordinary skill in the art may be
added to the multilayer film disclosed herein. Non-limiting examples of
anti-blocking agents include minerals (e.g., clays, chalk, and calcium
carbonate), synthetic silica gel (e.g., SYLOBLOC® from Grace Davison,
Columbia, Md.), natural silica (e.g., SUPER FLOSS® from Celite
Corporation, Santa Barbara, Calif.), talc (e.g., OPTIBLOC® from
Luzenac, Centennial, CO), zeolites (e.g., SIPERNAT® from Degussa,
Parsippany, N.J.), aluminosilicates (e.g., SILTON® from Mizusawa
Industrial Chemicals, Tokyo, Japan), limestone (e.g., CARBOREX® from
Omya, Atlanta, Ga.), spherical polymeric particles (e.g., EPOSTAR®,
poly(methyl methacrylate) particles from Nippon Shokubai, Tokyo, Japan
and TOSPEARL®, silicone particles from GE Silicones, Wilton, Conn.),
waxes, amides (e.g. erucamide, oleamide, stearamide, behenamide,
ethylene-bis-stearamide, ethylene-bis-oleamide, stearyl erucamide and
other slip agents), molecular sieves, and combinations thereof. The
mineral particles can lower blocking by creating a physical gap between
articles, while the organic anti-blocking agents can migrate to the
surface to limit surface adhesion. Where used, the amount of the
anti-blocking agent in the multilayer film can be from about greater than
0 to about 3 wt %, from about 0.0001 to about 2 wt %, from about 0.001 to
about 1 wt %, or from about 0.001 to about 0.5 wt % of the total weight
of the multilayer film. Some anti-blocking agents have been described in
Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner
Publications, Cincinnati, Ohio, 5th edition, Chapter 7, pages 585-600
(2001), which is incorporated herein by reference.

[0258] Optionally, one or more layers of the multilayer film disclosed
herein can comprise a plasticizer. In general, a plasticizer is a
chemical that can increase the flexibility and lower the glass transition
temperature of polymers. Any plasticizer known to a person of ordinary
skill in the art may be added to the multilayer film disclosed herein.
Non-limiting examples of plasticizers include mineral oils, abietates,
adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins,
citrates, epoxides, glycol ethers and their esters, glutarates,
hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives,
phosphates, phthalates, esters, polybutenes, ricinoleates, sebacates,
sulfonamides, tri- and pyromellitates, biphenyl derivatives, stearates,
difuran diesters, fluorine-containing plasticizers, hydroxybenzoic acid
esters, isocyanate adducts, multi-ring aromatic compounds, natural
product derivatives, nitriles, siloxane-based plasticizers, tar-based
products, thioeters and combinations thereof. Where used, the amount of
the plasticizer in the multilayer film can be from greater than 0 to
about 15 wt %, from about 0.5 to about 10 wt %, or from about 1 to about
5 wt % of the total weight of the multilayer film. Some plasticizers have
been described in George Wypych, "Handbook of Plasticizers," ChemTec
Publishing, Toronto-Scarborough, Ontario (2004), which is incorporated
herein by reference.

[0259] In some embodiments, one or more layers of the multilayer film
optionally comprise an antioxidant that can prevent the oxidation of
polymer components and organic additives in the multilayer film. Any
antioxidant known to a person of ordinary skill in the art may be added
to the multilayer film disclosed herein. Non-limiting examples of
suitable antioxidants include aromatic or hindered amines such as alkyl
diphenylamines, phenyl-α-naphthylamine, alkyl or aralkyl
substituted phenyl-α-naphthylamine, alkylated p-phenylene diamines,
tetramethyl-diaminodiphenylamine and the like (e.g. CHIMASSORB 2020);
phenols such as 2,6-di-t-butyl-4-methylphenol;
1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)benzene;
tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane
(e.g., IRGANOX® 1010, from Ciba Geigy, New York); acryloyl modified
phenols; octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX®
1076, commercially available from Ciba Geigy); phosphites and
phosphonites; hydroxylamines; benzofuranone derivatives; and combinations
thereof. Where used, the amount of the antioxidant in the multilayer film
can be from about greater than 0 to about 5 wt %, from about 0.0001 to
about 2.5 wt %, from about 0.001 to about 1 wt %, or from about 0.001 to
about 0.5 wt % of the total weight of the multilayer film. Some
antioxidants have been described in Zweifel Hans et al., "Plastics
Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th
edition, Chapter 1, pages 1-140 (2001), which is incorporated herein by
reference.

[0260] In other embodiments, one or more layers of the multilayer film
disclosed herein optionally comprise an UV stabilizer that may prevent or
reduce the degradation of the multilayer film by UV radiations. Any UV
stabilizer known to a person of ordinary skill in the art may be added to
the multilayer film disclosed herein. Non-limiting examples of suitable
UV stabilizers include benzophenones, benzotriazoles, aryl esters,
oxanilides, acrylic esters, formamidines, carbon black, hindered amines,
nickel quenchers, hindered amines, phenolic antioxidants, metallic salts,
zinc compounds and combinations thereof. Where used, the amount of the UV
stabilizer in the multilayer film can be from about greater than 0 to
about 5 wt %, from about 0.01 to about 3 wt %, from about 0.1 to about 2
wt %, or from about 0.1 to about 1 wt % of the total weight of the
multilayer film. Some UV stabilizers have been described in Zweifel Hans
et al., "Plastics Additives Handbook," Hanser Gardner Publications,
Cincinnati, Ohio, 5th edition, Chapter 2, pages 141-426 (2001), which is
incorporated herein by reference.

[0261] In further embodiments, one or more layers of the multilayer film
disclosed herein optionally comprise a colorant or pigment that can
change the look of the multilayer film to human eyes. Any colorant or
pigment known to a person of ordinary skill in the art may be added to
the multilayer film disclosed herein. Non-limiting examples of suitable
colorants or pigments include inorganic pigments such as metal oxides
such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides,
carbon black, organic pigments such as anthraquinones, anthanthrones, azo
and monoazo compounds, arylamides, benzimidazolones, BONA lakes,
diketopyrrolo-pyrroles, dioxazines, disazo compounds, diarylide
compounds, flavanthrones, indanthrones, isoindolinones, isoindolines,
metal complexes, monoazo salts, naphthols, b-naphthols, naphthol AS,
naphthol lakes, perylenes, perinones, phthalocyanines, pyranthrones,
quinacridones, and quinophthalones, and combinations thereof. Where used,
the amount of the colorant or pigment in the multilayer film can be from
about greater than 0 to about 10 wt %, from about 0.1 to about 5 wt %, or
from about 0.25 to about 2 wt % of the total weight of the multilayer
film. Some colorants have been described in Zweifel Hans et al.,
"Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati,
Ohio, 5th edition, Chapter 15, pages 813-882 (2001), which is
incorporated herein by reference.

[0262] Optionally, one or more layers of the multilayer film disclosed
herein can comprise a filler which can be used to adjust, inter alia,
volume, weight, costs, and/or technical performance. Any filler known to
a person of ordinary skill in the art may be added to the multilayer film
disclosed herein. Non-limiting examples of suitable fillers include talc,
calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass,
fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium
silicate, alumina, hydrated alumina such as alumina trihydrate, glass
microsphere, ceramic microsphere, thermoplastic microsphere, barite, wood
flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium
oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate,
titanium dioxide, titanates and combinations thereof. In some
embodiments, the filler is barium sulfate, talc, calcium carbonate,
silica, glass, glass fiber, alumina, titanium dioxide, or a mixture
thereof. In other embodiments, the filler is talc, calcium carbonate,
barium sulfate, glass fiber or a mixture thereof. Where used, the amount
of the filler in the multilayer film can be from about greater than 0 to
about 80 wt %, from about 0.1 to about 60 wt %, from about 0.5 to about
40 wt %, from about 1 to about 30 wt %, or from about 10 to about 40 wt %
of the total weight of the multilayer film. Some fillers have been
disclosed in U.S. Pat. No. 6,103,803 and Zweifel Hans et al., "Plastics
Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th
edition, Chapter 17, pages 901-948 (2001), both of which are incorporated
herein by reference.

[0263] Optionally, one or more layers of the multilayer film disclosed
herein can comprise a lubricant. In general, the lubricant can be used,
inter alia, to modify the rheology of the molten multilayer film, to
improve the surface finish of molded articles, and/or to facilitate the
dispersion of fillers or pigments. Any lubricant known to a person of
ordinary skill in the art may be added to the multilayer film disclosed
herein. Non-limiting examples of suitable lubricants include fatty
alcohols and their dicarboxylic acid esters, fatty acid esters of
short-chain alcohols, fatty acids, fatty acid amides, metal soaps,
oligomeric fatty acid esters, fatty acid esters of long-chain alcohols,
montan waxes, polyethylene waxes, polypropylene waxes, natural and
synthetic paraffin waxes, fluoropolymers and combinations thereof. Where
used, the amount of the lubricant in the multilayer film can be from
about greater than 0 to about 5 wt %, from about 0.1 to about 4 wt %, or
from about 0.1 to about 3 wt % of the total weight of the multilayer
film. Some suitable lubricants have been disclosed in Zweifel Hans et
al., "Plastics Additives Handbook," Hanser Gardner Publications,
Cincinnati, Ohio, 5th edition, Chapter 5, pages 511-552 (2001), both of
which are incorporated herein by reference.

[0264] Optionally, one or more layers of the multilayer film disclosed
herein can comprise an antistatic agent. Generally, the antistatic agent
can increase the conductivity of the multilayer film and to prevent
static charge accumulation. Any antistatic agent known to a person of
ordinary skill in the art may be added to the multilayer film disclosed
herein. Non-limiting examples of suitable antistatic agents include
conductive fillers (e.g., carbon black, metal particles and other
conductive particles), fatty acid esters (e.g., glycerol monostearate),
ethoxylated alkylamines, diethanolamides, ethoxylated alcohols,
alkylsulfonates, alkylphosphates, quaternary ammonium salts,
alkylbetaines and combinations thereof. Where used, the amount of the
antistatic agent in the multilayer film can be from about greater than 0
to about 5 wt %, from about 0.01 to about 3 wt %, or from about 0.1 to
about 2 wt % of the total weight of the multilayer film. Some suitable
antistatic agents have been disclosed in Zweifel Hans et al., "Plastics
Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th
edition, Chapter 10, pages 627-646 (2001), both of which are incorporated
herein by reference.

[0265] In further embodiments, one or more layers of the multilayer film
disclosed herein optionally comprise a cross-linking agent that can be
used to increase the cross-linking density of the multilayer film. Any
cross-linking agent known to a person of ordinary skill in the art may be
added to the multilayer film disclosed herein. Non-limiting examples of
suitable cross-linking agents include organic peroxides (e.g., alkyl
peroxides, aryl peroxides, peroxyesters, peroxycarbonates,
diacylperoxides, peroxyketals, and cyclic peroxides) and silanes (e.g.,
vinyltrimethoxysilane, vinyltriethoxysilane,
vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane,
vinylmethyldimethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane).
Where used, the amount of the cross-linking agent in the multilayer film
can be from about greater than 0 to about 20 wt %, from about 0.1 to
about 15 wt %, or from about 1 to about 10 wt % of the total weight of
the multilayer film. Some suitable cross-linking agents have been
disclosed in Zweifel Hans et al., "Plastics Additives Handbook," Hanser
Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 14, pages
725-812 (2001), both of which are incorporated herein by reference.

[0266] In certain embodiments, one or more layers of the multilayer film
optionally comprise a wax, such as a petroleum wax, a low molecular
weight polyethylene or polypropylene, a synthetic wax, a polyolefin wax,
a beeswax, a vegetable wax, a soy wax, a palm wax, a candle wax or an
ethylene/α-olefin interpolymer having a melting point of greater
than 25° C. In certain embodiments, the wax is a low molecular
weight polyethylene or polypropylene having a number average molecular
weight of about 400 to about 6,000 g/mole. The wax can be present in the
range from about 10% to about 50% or 20% to about 40% by weight of the
total composition.

[0267] The ethylene/α-olefin interpolymer disclosed herein can be
used to prepare the multilayer films by any known film processes. In some
embodiments, the ethylene/α-olefin interpolymer is used in the
sealant layers of the multilayer films. Some non-limiting example of
suitable film processes include blown film extrusion, cast film process,
and the laminate film process.

Blown Film Extrusion Process

[0268] In general, extrusion is a process by which a polymer is propelled
continuously along a screw through regions of high temperature and
pressure where it is melted and compacted, and finally forced through a
die. The extruder can be a single screw extruder, a multiple screw
extruder, a disk extruder or a ram extruder. Several types of screw can
be used. For example, a single-flighted screw, double-flighted screw,
triple-flighted screw, or other multi-flighted screw can be used. The die
can be a film die, blown film die, sheet die, pipe die, tubing die or
profile extrusion die. In a blown film extrusion process, a blown film
die for monolayer or multilayer film can be used. The extrusion of
polymers has been described in C. Rauwendaal, "Polymer Extrusion", Hanser
Publishers, New York, N.Y. (1986); and M. J. Stevens, "Extruder
Principals and Operation," Ellsevier Applied Science Publishers, New
York, N.Y, (1985), both of which are incorporated herein by reference in
their entirety.

[0269] In a blown film extrusion process, one or more polymers can be
first fed into a heated barrel containing a rotating screw through a
hopper, and conveyed forward by the rotating screw and melted by both
friction and heat generated by the rotation of the screw. The polymer
melt can travel through the barrel from the hopper end to the other end
of the barrel connected with a blown film die. Generally, an adapter may
be installed at the end of the barrel to provide a transition between the
blown film die and the barrel before the polymer melt is extruded through
the slit of the blown film die. To produce multilayer films, an equipment
with multiple extruders joined with a common blown film die can be used.
Each extruder is responsible for producing one component layer, in which
the polymer of each layer can be melted in the respective barrel and
extruded through the slit of the blown film die. After forced through the
blown film die, the extrudate can be blown up by air from the center of
the blown film die like a balloon tube. Mounted on top of the die, a
high-speed air ring can blow air onto the hot film to cool it. The cooled
film tube can then pass through nip rolls where the film tube can be
flattened to form a flat film. The flat film can be then either kept as
such or the edges of the lay-flat can be slit off to produce two flat
film sheets and wound up onto reels for further use. The volume of air
inside the tube, the speed of the nip rollers and the extruders output
rate generally play a role in determining the thickness and size of the
film.

[0270] In some embodiments, the barrel has a diameter of about 1 inch to
about 10 inches, from about 2 inches to about 8 inches, from about 3
inches to about 7 inches, from about 4 inches to about 6 inches, or about
5 inches. In other embodiments, the barrel has a diameter from about 1
inch to about 4 inches, from about 2 inches to about 3 inches or about
2.5 inches. In certain embodiments, the barrel has a length to diameter
(L/D) ratio from about 10:1 to about 30:1, from about 15:1 to about 25:1,
or from about 20:1 to about 25:1. In further embodiments, the L/D ratio
is from about 22:1 to about 26:1, or from about 24:1 to about 25:1.

[0271] The barrel can be divided into several temperature zones. The zone
that is closest to the hopper end of the barrel is usually referred to as
Zone 1. The zone number increases sequentially towards the other end of
the barrel. In some embodiments, there are 1, 2, 3, 4, 5, 6, 7, 8, 9, or
10 temperature zones in a barrel. In other embodiments, there are more
than 10, more than 15, more than 20 temperature zones in a barrel. The
temperature of each temperature zone in the barrel can range from about
50° F. to about 1000° F., from about 80° F. to about
800° F., from about 100° F. to about 700° F. from
about 150° F. to about 600° F., from about 200° F.
to about 500° F., or from about 250° F. to about
450° F. In some embodiments, the barrel temperature increases
sequentially from the first Zone to the last Zone. In other embodiments,
the barrel temperature remains substantially the same throughout the
barrel. In other embodiments, the barrel temperature decreases from the
first Zone to the last Zone. In further embodiments, the barrel
temperature changes randomly from one zone to another.

[0272] In some embodiments, the die can also be heated to a specific
temperature, ranging from about 250° F. to about 700° F.,
from about 300° F. to about 600° F., from about 350°
F. to about 550° F., from about 400° F. to about
500° F. In other embodiments, the die temperature ranges from
about 425° F. to about 475° F. or from 430° F. to
about 450° F.

[0273] The adapter temperature can be between the die temperature and the
temperature of the last zone. In some embodiments, the adapter
temperature is from about 200° F. to about 650° F., from
about 250° F. to about 600° F., from about 300° F.
to about 550° F., from about 350° F. to about 500°
F., and from about 400° F. to about 450° F.

Cast Film Process

[0274] The cast film process involves the extrusion of polymers melted
through a slot or flat die to form a thin, molten sheet or film. This
film can then be "pinned" to the surface of a chill roll by a blast of
air from an air knife or vacuum box. The chill roll can be water-cooled
and chrome-plated. The film generally quenches immediately on the chill
roll and can subsequently have its edges slit prior to winding.

[0275] Because of the fast quench capabilities, a cast film generally is
more glassy and therefore has a higher optic transmission than a blown
film. Further, cast films generally can be produced at higher line speeds
than blown films. Further, the cast film process may produce higher scrap
due to edge-trim, and may provide films with very little film orientation
in the cross-direction.

[0276] As in blown film, co-extrusion can be used to provide multilayer
films disclosed herein. In some embodiments, the multilayer films may
have additional functional, protective, and decorative properties than
monolayer films. Cast films can be used in a variety of markets and
applications, including stretch/cling films, personal care films, bakery
films, and high clarity films.

[0277] In some embodiments, a cast film line may comprise an extrusion
system, a casting machine, and a winder. Optionally, the cast film line
may further comprise a gauging system, a surface treatment system and/or
an oscillation stand. The cast film die can be generally positioned
vertically above the main casting roll and the melt can be pinned against
the casting roll with the use of an air knife and/or vacuum box.

[0278] The casting machine is generally designed to cool the film and
provide the desired surface finish on the film. In some embodiments, the
casting machine comprises two casting rolls. The main casting roll may be
used to provide initial cooling and surface finish on the film. The
secondary casting roll can cool the opposite side of the film to provide
uniformity in the film. For embossed film applications, the casting roll
may have an engraved pattern and can be nipped with a rubber roll.
Optionally, a water bath and squegee roll can be used for cooling the
surface of the rubber roll.

[0279] The casting rolls can be double shell style with spiral baffle, and
may have an internal flow design to maintain superior temperature
uniformity across the width of the web. Optionally, cold water from the
heat transfer system can be circulated to cool the rolls.

[0280] Once cast, the film can optionally pass through a gauging system to
measure and control thickness. Optionally, the film can be
surface-treated either by a corona or a flame treater and passed through
an oscillating station to randomize any gauge bands in the final wound
product. Before the cast film enters the winder, the edges can be trimmed
for recycling or disposal. In some embodiments, automatic roll and shaft
handling equipment are sometimes provided for winders with short cycle
times.

Laminate Film Process

[0281] In the laminate film process for making a multilayer film, the
polymers for each of the layers are independently processed by an
extruder to polymer melts. Subsequently, the polymer melts are combined
in layers in a die, formed into a casting, and quenched to the solid
state. This casting may be drawn uniaxially in the machine direction by
reheating to from about 50° C. to about 200° C. and
stretching from about 3 times to about 10 times between rolls turning at
different speeds. The resulting uniaxially oriented film can then be
oriented in the transverse direction by heating to from about 75°
C. to about 175° C. in an air heated oven and stretching from
about 3 times to about 10 times between diverging clips in a tenter
frame.

[0282] Alternately, the two direction stretching may take place
simultaneously in which case the stretching may be from about 3 times to
about 10 times in each direction. The oriented film can be cooled to near
ambient temperature. Subsequent film operations, such as corona treatment
and metalization, may then be applied. Alternatively, the layers of the
multilayer film can be brought together in stages rather than through the
same die. In some embodiments, the base layer is cast initially, and then
the sealant layer can be extrusion coated onto the base layer casting. In
other embodiments, the sealant layer is cast initially, and then the base
layer can be extrusion coated onto the sealant layer casting. In further
embodiments, the sealant layer is cast initially, and then the tie layer
and base layer can be extrusion coated onto the sealant layer casting
sequentially or simultaneously. In further embodiments, the base layer is
cast initially, and then the tie layer and sealant layer can be extrusion
coated onto the base layer casting sequentially or simultaneously. This
extrusion coating step may occur prior to MD orientation or after MD
orientation.

[0283] If desirable, the multilayer film can be coated with a metal such
as aluminum, copper, silver, or gold using conventional metalizing
techniques. The metal coating can be applied to the base layer or sealant
layer by first corona treating the surface of the base layer or sealant
layer and then applying the metal coating by any known method such as
sputtering, vacuum deposition, or electroplating.

[0284] If desirable, other layers may be added or extruded onto the
multilayer film, such an adhesive or any other material depending on the
particular end use. For example, the outer surface of the multilayer
film, such as the base layer or sealant layer, may be laminated to a
layer of cellulosic paper.

[0290] A Battenfeld Gloucester Extrol 6032 Process Control System with CRT
display screen and printer was employed with a Battenfeld Gloucester
hopper loading system with three hoppers. A six inch 3 layer co-extrusion
Macro die and air ring was employed along with a die gap of 70 mil. A 10
HP Buffalo blower with variable speed control for air ring cooling air
was used in conjunction with piped in block chilled water for chilled air
in air ring. Other equipment included a Gloucester tower with Sano
collapsing frame, bubble sizing cage and bubble enclosure for 18 to 40
inch lay flat, with nip rolls 54'' long, adjustable bubble cage
elevators, 15 HP blower on collapsing frame, a Gloucester 116 dual turret
winder with 52'' lug type expanding shafts with automatic cut-over, a 200
CFM fan coil heat exchanger from AEC, a Battenfeld Gloucester Internal
Bubble Cooling (IBC) System, a Battenfeld Gloucester Cooling System for
the IBC System.

[0291] Two screws for the 21/2'' Egan Extruders were used. The core is a
DSB II manufactered by Davis Standard, has a bar flight type, a metering
depth of 0.204 inches, a feed depth of 0.48 inches, a comp. ratio of
2.35, a MAD mixer type, a 0.04 inch mixer clear, a feed length of 5
inches, a tran. length of 14 inches and a meter length of 2 inches. The
outside screw for the 21/2'' Egan Extruder is a SF High shear (with 2
interchangeable mixers) manufactured by New Castle, has an SF flight
type, a metering depth of 0.104 inches, a feed depth of 0.3 inches, a
comp. ratio of 2.88, a twisted Egan/Z-mixer type, a 0.0345 mixer clear, a
feed length of 6 inches, a tran. length of 6 inches and a meter length of
12 inches.

[0292] The screw for the 2'' Johnson Extruder is manufactered by Johnson,
has an SF flight type, a metering depth of 0.17 inches, a feed depth of
0.425 inches, a comp. ratio of 2.5, a MAD mixer type, a 0.035 inch mixer
clear, a feed length of 5 inches, a tran. length of 8 inches and a meter
length of 8 inches.

[0293] Precision Air Convey Corporation Trim Removal System model number
BC3-06-22A and Western Polymers Entrac Dual Iris for 6 inch monolayer die
Model Number SAT II 0601 were also employed.

[0294] Three-layer films were made by a blown film extrusion process using
the equipment above. One extruder was used for making the sealant layer,
which has a barrel diameter of 2.5 inch and a single-flight-high-shear
screw with a screw compression ratio of 2.88. A second extruder was used
for making the tie layer, which has a barrel diameter of 2.5 inch and a
modified-double-mix screw with a screw compression ratio of 3.64. A third
extruder was used for making the base layer, which has a barrel diameter
of 2.0 inch and a single-flighted screw with a screw compression ratio of
2.5. Each barrel has a length to diameter (L/D) ratio of 24:1 and has
four temperature Zones, i.e., Zone 1, Zone 2, Zone 3, and Zone 4. Zone 1
is closest to the hopper end and Zone 4 is closest to the die end. The
barrel diameter was 2.5 inch. All of barrels have smooth surfaces. The
chill roll temperature was about 15° C. The Nip Pressure was about
13 kg/cm. The Extrusion Rate was about 35 kg/hr.

[0295] The temperatures profiles of each extruder is listed in Table 8
below.

[0296] According to the type of polymers used, the following films were
made.

Example BB

[0297] Example BB comprised a sealant layer made of 100% polymer of
Example 16, a tie layer made of 90% ATTANE® 4201 G, a linear low
density polyethylene (LLDPE) having an I2 of 1 and a density of
0.912 g/cc available at Dow Chemical, 10% of AMPLIFY® GR 205, a maleic
anhydride-grafted polyethylene available at Dow Chemical, and a base
layer made of 100% ULTRAMID® C33L, a polyamide copolymer available at
BASF. The total thickness of the film was 3.5 mils. The base layer had a
thickness of 0.875 mils, constituting 25% of the total thickness. The tie
layer had a thickness of 1.75 mils, constituting 50% of the total
thickness. The sealant layer had a thickness of 0.875, constituting 25%
of the total thickness.

Example CC

[0298] Example CC comprised a sealant layer made of 100% polymer of
Example 17, a tie layer made of 90% ATTANE® 4201 G, a linear low
density polyethylene (LLDPE) having an I2 of 1 and a density of
0.912 g/cc available at Dow Chemical, 10% of AMPLIFY® GR 205, a maleic
anhydride-grafted polyethylene available at Dow Chemical, and a base
layer made of 100% ULTRAMID® C33L, a polyamide copolymer available at
BASF. The total thickness of the film was 3.5 mils. The base layer had a
thickness of 0.875 mils, constituting 25% of the total thickness. The tie
layer had a thickness of 1.75 mils, constituting 50% of the total
thickness. The sealant layer had a thickness of 0.875, constituting 25%
of the total thickness.

Comparative Example DD

[0299] Comparative Example DD comprised a sealant layer made of 100%
AFFINITY® PL 1880G having an I2 of 1 and a 0.902 g/cc density, a
tie layer made of 90% ATTANE® 4201 G, a linear low density
polyethylene (LLDPE) having an I2 of 1 and a density of 0.912 g/cc
available at Dow Chemical, 10% of AMPLIFY® GR 205, a maleic
anhydride-grafted polyethylene available at Dow Chemical, and a base
layer made of 100% ULTRAMID® C33L, a polyamide copolymer available at
BASF. The total thickness of the film was 3.5 mils. The base layer had a
thickness of 0.875 mils, constituting 25% of the total thickness. The tie
layer had a thickness of 1.75 mils, constituting 50% of the total
thickness. The sealant layer had a thickness of 0.875, constituting 25%
of the total thickness.

Comparative Example EE

[0300] Comparative Example EE comprised a sealant layer made of 100%
EXACT® 3132 having an I2 of 1.02 and 0.900 g/cc density, a tie
layer made of 90% ATTANE® 4201G, a linear low density polyethylene
(LLDPE) having an I2 of 1 and a density of 0.912 g/cc available at
Dow Chemical, 10% of AMPLIFY® GR 205, a maleic anhydride-grafted
polyethylene available at Dow Chemical, and a base layer made of 100%
ULTRAMID® C33L, a polyamide copolymer available at BASF. The total
thickness of the film was 3.5 mils. The base layer had a thickness of
0.875 mils, constituting 25% of the total thickness. The tie layer had a
thickness of 1.75 mils, constituting 50% of the total thickness. The
sealant layer had a thickness of 0.875, constituting 25% of the total
thickness.

Example II

[0301] Example II was a two-layer film. The base layer was made of
Biaxially Oriented Polypropylene (BOPP) with a thickness of 0.5 mils. The
sealant layer was made of the polymer of Example 18 with a thickness of
0.75 mils.

Example JJ

[0302] Example JJ was a three-layer film. The inside base layer was made
of PET or Nylon with a thickness of 2 mils. The outside sealant layer was
made of the polymer of Example 19 with a thickness of 2 mils. The tie
layer between the sealant layer and the base layer was poly(ethylene
vinyl acetate) with a thickness of 1 mils.

Example KK

[0303] Example KK was a four-layer film. The first layer was a base layer
made of polycarbonates with a thickness of 0.1 mils. The second layer was
a tie layer made of low density polyethylene (LDPE) with a thickness of
0.3 mils. The third layer was a sealant layer made of the polymer of
Example 20 with a thickness of 0.7 mils.

Example LL

[0304] Example LL was a five-layer film. The first layer was a base layer
made of polystyrene with a thickness of 0.3 mils. The second layer was a
tie layer made of acid-modified polyolefin polymer with a thickness of 1
mil. The third layer was a middle layer made of vinylidene chloride
(VDC)-methyl acrylate(MA) copolymer with a thickness of 0.5 mils. The
fourth layer was a tie layer also made of acid-modified polyolefin
polymer with a thickness of 1 mil. The fifth layer was a sealant layer
made of the polymer of Example 21 with a thickness of 1.8 mils.

[0305] For examples BB-EE, the extruder profiles are approximately the
same as shown in Table 8. For Examples MM through PP below, the extruder
profiles are shown in Table 8a below:

[0306] Example MM comprised a sealant layer made of 100% polymer of
Example 20, a tie layer made of 90% DOWLEX® 2038.68G, having a 1 I2
and a 0.935 g/cc density, a linear low density polyethylene (LLDPE)
available at Dow Chemical, 10% of AMPLIFY® GR 205, a maleic
anhydride-grafted polyethylene available at Dow Chemical, and a base
layer made of 100% ULTRAMID® C33L, a polyamide copolymer available at
BASF. The total thickness of the film was 3.5 mils. The base layer had a
thickness of 0.875 mils, constituting 25% of the total thickness. The tie
layer had a thickness of 1.75 mils, constituting 50% of the total
thickness. The sealant layer had a thickness of 0.875, constituting 25%
of the total thickness.

Example NN

[0307] Example NN comprised a sealant layer made of 100% polymer of
Example 21, a tie layer made of 90% DOWLEX® 2038.68G, a linear low
density polyethylene (LLDPE) available at Dow Chemical, 10% of
AMPLIFY® GR 205, a maleic anhydride-grafted polyethylene available at
Dow Chemical, and a base layer made of 100% ULTRAMID® C33L, a
polyamide copolymer available at BASF. The total thickness of the film
was 3.5 mils. The base layer had a thickness of 0.875 mils, constituting
25% of the total thickness. The tie layer had a thickness of 1.75 mils,
constituting 50% of the total thickness. The sealant layer had a
thickness of 0.875, constituting 25% of the total thickness.

Comparative Example OO

[0308] Comparative Example OO comprised a sealant layer made of 100%
polymer of ATTANE® 4201G, a tie layer made of 90% DOWLEX® 2038.68G,
a linear low density polyethylene (LLDPE) available at Dow Chemical, 10%
of AMPLIFY® GR 205, a maleic anhydride-grafted polyethylene available
at Dow Chemical, and a base layer made of 100% ULTRAMID® C33L, a
polyamide copolymer available at BASF. The total thickness of the film
was 3.5 mils. The base layer had a thickness of 0.875 mils, constituting
25% of the total thickness. The tie layer had a thickness of 1.75 mils,
constituting 50% of the total thickness. The sealant layer had a
thickness of 0.875, constituting 25% of the total thickness.

Comparative Example PP

[0309] Comparative Example PP comprised a sealant layer made of 100%
polymer of EXCEED® 1012CA, a 1 I2, 0.912 g/cc density LLDPE available
from ExxonMobil Corporation, a tie layer made of 90% DOWLEX® 2038.68G,
a linear low density polyethylene (LLDPE) available at Dow Chemical, 10%
of AMPLIFY® GR 205, a maleic anhydride-grafted polyethylene available
at Dow Chemical, and a base layer made of 100% ULTRAMID® C33L, a
polyamide copolymer available at BASF. The total thickness of the film
was 3.5 mils. The base layer had a thickness of 0.875 mils, constituting
25% of the total thickness. The tie layer had a thickness of 1.75 mils,
constituting 50% of the total thickness. The sealant layer had a
thickness of 0.875, constituting 25% of the total thickness.

Hot Tack Strength

[0310] Hot tack strength of BB-PP was measured on a J&B type Hot Tack
testing apparatus following ASTM F 1921, Method B. As the thickness of
the sealant layer was less than 1 mil, the dwell time was 500 ms. The
seal pressure was 27.5 N/cm2. Test specimens were 1 inch in width
and were conditioned as specified by ASTM E 171. All specimens tested
failed in an adhesive failure mode. The results are listed in Table 9
below.

[0311] The average hot tack force (N) of multilayer films of BB, CC, DD,
and EE at different temperatures is shown in FIG. 30. It can be seen that
BB and CC that comprises the inventive polymers have improved hot tack
properties over DD and EE that comprise comparative polymers. The average
hot tack force (N) of multilayer films of examples MM, NN, OO, and PP are
shown in FIG. 31. It can also be seen that Example NN has improved hot
tack properties over Example OO and PP.

Oriented Films

[0312] A 25 mil thick film was made using the ethylene/α-olefin
interpolymer of Example 22 and subsequently biaxially stretched using a
Bruckner biaxial Tenter frame labscale device approximately 4.5×in
each direction for a film guage of about 1.25 mil. The film was oriented
at various temperatures and the instrumented Dart impact was tested at
ambient temperature using 0.5 inch diameter dart size, a clamp diameter
films/1.5 in clamp, and a speed of 3.4 m/s. The results for the oriented
film comprising the interpolymer of example 22 is shown in Table 10. The
above procedure was conducted again except that Comparative Polymer G was
substituted for the polymer of Example 22. The results for the oriented
film comprising the interpolymer of Comparative Polymer G is shown in
Table 11.

[0393] The calculations involved locating four stationary points on the
potential energy surface (see Diagram 1). Standard optimizations and
defaults within the Gaussian98 program were utilized which included the
Berny optimizer in redundant internal coordinates as described in Peng,
C.; Ayala, P. Y.; Schlegel, H. B. Frisch, M. J. J. Comp. Chem. 1996, 17,
49; and Peng, C.; Schlegel, H. B. Israel. J. Chem. 1994, 33, 449. The
four structures located were the transition state for ethylene inserting
into the M-aryl or M-hydrocarbyl bond of the original species (1), the
transition state for ethylene inserting in the polymeryl chain of the
original species (2), the product of inserting into the aryl or
hydrocarbyl group (3), and the product of inserting into the polymeryl
chain (4). The stationary points defined as transition states were
confirmed by one and only one imaginary frequency (corresponding to the
reaction coordinate) as determined from mass-weighting of the eigenvalues
from the diagonalization of the second derivative or Hessian matrix. The
two products, 3 and 4, have no imaginary frequencies upon this analysis.

[0394] In examples involving ethylene/octene, more than one potential
`inserted` catalyst could be formed. Diagram 2 depicts the four possible
octene inserted catalysts from one face. These four unique catalysts each
could create polymer with different properties such as molecular weight
and comonomer incorporation.

[0395] Insertions can occur on the top and bottom faces of the catalyst
and these can be unique depending on the overall symmetry of the initial
catalyst (Diagram 3). For the specific catalyst below, insertions into
the top and bottom faces lead to unique isomers. Thus for ethylene/octene
polymerizations, up to ten unique `inserted` catalysts are possible. The
aforementioned calculations indicate that not all are favorable, but
certainly more than one is possible. As described above, the Applicants
have determined that different conditions can be used to favor one or
some over others.

[0396] Based on catalyst activity such as the one above, barriers
important for the polymerization may be estimated. If insertion into the
aryl or hydrocarbyl is less than 10 kcal/mol higher than insertion into
the alkyl, this reaction should occur during the polymerization cycle.
From Diagrams 1 and 4, this implies that TS 1 lies no higher than 10
kcal/mol above TS 2. It is preferable that this difference is less than 5
kcal/mol and even more preferable that insertion into the aryl or
hydrocarbyl is less than insertion into the alkyl. Insertion into the
alkyl is not a reversible process, but to avoid reversibility of
insertion into the aryl or hydrocarbyl, the product of insertion into the
aryl or hydrocarbyl cannot lie more than 5 kcal/mol above insertion into
the alkyl. From Diagrams 1 and 4, this implies that Product 3 lies no
higher than 5 kcal/mol above Product 4. However, it is preferable that
this difference is less and even more preferable that the product of aryl
or hydrocarbyl insertion is lower than the product of alkyl insertion.
Diagram 4 depicts a potential energy surface of the two processes.

[0397] One skilled in the art may apply the above principles in selecting
reaction conditions and catalyst to achieve a desired controlled
molecular weight.